TW536551B - Carbon black and process for producing the same - Google Patents

Abstract

A carbon black having an average particle size of at most 13 nm, Dmod of at most 80 nm, a D1/2/Dmod ratio of at most 0.6 and at least pH 5.

Description

536551 A7 B7_ V. Description of the invention (). (Please read the precautions on the back before filling out this page.) This invention relates to a carbon black that can be used for filling materials, reinforcing materials, conductive materials, and pigments. An extremely effective method for producing carbon black by controlling its physical properties. 〇It is known that carbon black can be used for various purposes such as pigments, fillers, reinforcing pigments, and weather resistance improvers. Among its manufacturing methods, generally known methods are in a cylindrical carbon black manufacturing furnace. When the gas and fuel containing oxygen are introduced in the direction of the furnace axis or the wiring direction in the first reaction zone area, when the high-temperature combustion gas obtained by this combustion is moved to the second reaction zone area sequentially arranged in the furnace shaft direction, A furnace-type manufacturing method in which a hydrocarbon raw material is introduced into this gas stream to generate carbon black, and the reaction gas stream is rapidly cooled in a third reaction zone to stop the reaction. Carbon blacks generally used as colorants in resin colorants, printing inks, and coatings should have excellent blackness, dispersibility, gloss, and tinting power, and carbon blacks mainly used as vehicle tire reinforcements should be required to have excellent Wear resistance. The carbon black particles printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs usually exist in the form of fused particles like fish skewers, and each spherical particle can be referred to as the mountain or valley of nine children. The particle size of this single particle is closely related to the performance of various uses, such as reinforcement or blackness (Carbon Black Fact Sheet 3rd Edition, I • Overall Introduction, page 7). Carbon black particles can be directly measured from photographs obtained by tens of thousands of times photographing with an electron microscope capable of decomposing at least 1.5 to 2 nm. The so-called carbon black particle size or primary particle size refers to the carbon black particle size measured according to this method. The level of this particle size is in the range of 10 to 300 nm, which is microparticles. This paper is applicable to China. National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7 V. Description of invention (2). Or granular area. When carbon black is used as a black material, its blackness or tinting power has a considerable relationship with the primary particle size, for example, the smaller the particle size, the higher the relationship. Other related relationships are disclosed in, for example, Japanese Patent Application Laid-Open No. Sho 50-6 8 9 2. In addition, when a smaller particle size is used as a reinforcing agent for automobile tires, it also has higher abrasion resistance. When carbon black is used as a black raw material, ultrafine carbon black with a particle size of 15 nm or less has high blackness and is therefore suitable for advanced paints or advanced resin colorants. Generally, the carbon black of this grade is called H C C (High Color Channel) by the pipe method, and HCF (High Color Furnace) by the furnace method. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Among the small particle sizes, there are ultrafine carbon blacks with particles smaller than 1 4 nm, which has extremely high blackness, and It is suitable for the highest-grade paints or the highest-grade resin colorants. Among them, almost all of the commercial products are those produced by the pipeline method. In the pipe method, ultrafine particles having a particle size of 1 to 14 nm can be produced in a manner that the particle diameter distribution is extremely concentrated, and can exhibit extremely high degree of blackness. Especially in the field of high-grade paints or high-grade resin colorants, carbon black with the highest blackness can be developed, so it has a tendency to monopolize the market. In order to obtain carbon black with a small particle diameter in the furnace method, firstly, it is necessary to spray hydrocarbon with a high-speed gas flow provided in a gas blocking part of the second reaction zone to cause gas movement and thermal energy to form liquid-supplied raw materials into mist The chemical formula has an effect. For example, in Japanese Patent Publication No. 5 4 — 10 3 5 8, it is recorded that liquid hydrocarbon is burned in a condition that can be efficiently atomized and dispersed. CNS) A4 specification (210X297 mm) ^ 536551 A7 B7 V. Description of the invention (3) The body flow rate should be at least Mach 3.5, preferably within the range of 0.4 to 0.8. In order to more effectively atomize and disperse the liquid material, the flow rate at the position where the liquid hydrocarbon material is introduced should be as fast as possible. However, in order to make the flow rate at the position where the liquid hydrocarbon material is introduced is faster, For example, when the flow velocity of the introduction position of the hydrocarbon raw material is close to the speed of sound, the furnace will produce a great pressure loss. Especially when spraying hydrocarbon raw materials in a long choke tube, the pressure loss is extremely large, and the capabilities of peripheral equipment such as the blowing of combustion air must be greatly improved. In another aspect, when the combustion gas is introduced into the choke tube at a high speed, parts of the choke tube that are directly or indirectly contacted by the combustion gas will be damaged by the energy of the gas movement. Among them, the velocity at which the flow rate of the combustion gas introduced with the hydrocarbon raw material does not cause great pressure loss or cause great damage to the device is in the range of Mach 0.8 to 1. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). It is known that when the amount of raw material oil injected into the amount of combustion gas is small, carbon black with a small particle size can be obtained. However, when the proportion of the feed oil is too small, the productivity of carbon black is reduced. In a method which does not reduce productivity, it is known that if the temperature of the gas in the raw material oil injection region is increased, the carbon black having a small particle diameter can be produced more efficiently. Therefore, in the method for manufacturing the carbon black of the furnace, the gas injected into the raw material oil generally retains a part of oxygen, so that the raw material oil itself is partially burned to raise the temperature of the carbon black generating region. However, this method makes a part of the injected raw material oil fail to form carbon black and is used for the combustion reaction, so the production of carbon black is not good. Therefore, according to the technology of the previous furnace method, it is difficult to stably produce substances with a particle size of 1 1 to 1 4 nm. For example, even if the paper size can be made to the Chinese National Standard (CNS) A4 specification (210X297) Gong) -6-536551 A7 B7_ V. Description of the invention (4) Particles below the particle size, but the particle size distribution will be extremely wide, and can not reach the blackness like the pipe method. In addition, in order to obtain a substance with a small particle size, the amount of hydrocarbon raw materials charged into the furnace must be extremely small in terms of the amount of combustion gases generated in the furnace. This also makes the product yield_ Extremely low. -In addition, in order to obtain a substance with a high degree of blackness according to the conventional furnace method technology, in addition to the small particle size, the oil absorption of DBP as an indicator of aggregate development described below must be reduced. Generally, the method of reducing the oil absorption of DBP is, for example, adding an alkali metal or a solution thereof to the raw material oil, and introducing it into a combustion zone or a reaction zone. When the oil absorption of DBB is reduced, a thinner or a resin added to the coating is particularly added. In some cases, dispersibility or flowability may be deteriorated. To date, there have been several reports of attempts to make carbon black equivalent to pipe black by the furnace method. For example, Japanese Unexamined Patent Publication No. 5 4-7 6 3 2 describes a method of gasifying a hydrocarbon raw material to be supplied to a furnace, and an EM average particle diameter (equivalent to the average particle diameter) of 9 nm and an EM particle diameter can be obtained. Standard error is 5.7nm, carbon black with a ratio of BET specific surface area / EM specific surface area 1 of 1. 25; average particle diameter of EM is 14nm, standard error of EM particle diameter is 5.5 nm, BET specific surface area / EM specific surface area Carbon black with a ratio 値 of 1 · 2 5. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). However, in addition to the particle size, this content is about the characteristics of carbon black, especially the above-mentioned aggregates that can control the blackness. There is no record or description of the diameter and distribution status. In addition, judging from the result that the ratio BET specific surface area / EM specific surface area 値 is equal to or less than 1.3, it is presumed that the proportion of polycyclic aromatic hydrocarbons is large, and safety is not sufficient as described later. In addition, in the paper method that can produce ultrafine particles with high blackness carbon black by the pipe method, the Chinese National Standard (CNS) A4 specification (210 × 297 mm)-536551 A7 B7 V. Description of the invention (5) In order to produce an oxygen environment, there are disadvantages that the yield of the product obtained in the manufacturing step itself is degraded and the productivity is reduced. The pipe black of small particles produced by the pipe method, for example, "F W 2 0 0" (trade name, manufactured by Texark), has a particle size of 13 nm (catalog-recorded number). -However, this small particle pipe black produced by the pipe method, because it is produced in an oxygen environment, the carbon black itself shows acidity. Because of this, there are several important disadvantages. That is, (1) when the resin is added, the prepared resin composition is extremely liable to deteriorate; (2) when the rubber is added, the rubber composition produced has reduced abrasion resistance, and (3) a water-based coating composition is produced Carbon black in the coating composition is prone to agglomeration, and other basic disadvantages. * It is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. It is not only the average size of the primary particle size, but also the distribution of the primary particle size. It has a great influence, so its primary particle size distribution is better in a more concentrated way. Generally, the smaller the average particle size is, the more concentrated the distribution. The method of making the primary particle size distribution more concentrated is also revealed. For example, the length of the choke tube described in Japanese Patent Application Laid-Open No. 3-3 3 1 6 7 has a better result on the formation reaction of carbon black, and the vortex generated by the enlarged part of the choke tube outlet can be improved, which can be used in carbon. The so-called "inverse mixing" is prevented during the black generation reaction, and carbon black with a relatively concentrated particle size distribution can be obtained. The factors that can affect the primary particle size and the characteristics of carbon black are aggregates. Aggregate-8- (Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7__ 5. The size of the invention description (6) is added in The traction stress or extrusion characteristics when rubber is used, has great influence on the dispersibility, blackness, viscosity, etc. when it is added to the ink or coating diluent and resin. Carbon black is finally composed of several aggregates composed of primary particles. The control of the size or shape of this aggregate / collection is related to the method of controlling the characteristics of carbon black. Therefore, the control of primary particle size is extremely important. Significance. The effect of aggregates is performed in a quantitative manner such as particle size or distribution. The particle size of the aggregates can be measured by a technique for measuring various particle sizes, and the size of the aggregates measured in this manner is the aggregate diameter. Aggregates have a great influence on the characteristics of carbon black. So far, the characteristics of carbon black are mostly considered to be caused by the primary particle size, but it is more correct to say that the effect of the diameter of the aggregate is more accurate. For example, in terms of optical properties such as tinting strength or dynamic viscoelastic properties or reinforcing properties of the rubber composition, the diameter of the aggregate can achieve a larger effect. When it is used for resin coloring, it can be known that the smaller the aggregate diameter, the higher the blackness. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). In addition to the aggregate diameter of these particles as aggregate indicators, for example, there are still indicators such as DBP oil absorption and cDBP. The effect of cDBP on blackness or dispersibility is also a well-known fact. When c D B P decreases, the blackness increases and dispersibility also decreases. Generally, the method of reducing the aggregate diameter is performed by, for example, adding an alkali metal or a solution thereof to the feedstock oil, or introducing it into a combustion zone or a reaction zone. As the number showing the index of the diameter distribution of the aggregates, the half-width of the equivalent diameter of the Stokes equivalent particle size distribution of the aggregates in the centrifugal sedimentation method D 1/2 is used. Paper size with maximum frequency is applicable to Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) -9- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 536551 A7 B7 _ V. Description of the invention (7) · grams When the ratio of the equivalent particle size Dmod iD i / 2 / is controlled to a certain range, the properties of rubber additives with carbon black can be improved. For example, Japanese Patent No. 2 6 9 5 7 0 1 discloses a kind of carbon black with improved processing and granulation function, high abrasion resistance, and modified-good traction, with a CTAB of 162m2 / g, 12 number is 206 mg / g, N2SA is 197 m2 / g, Tint 値 is 154%, cDBP is 100 cc / 100 g, DBP is 133 cc / 100 g »ADBP (ADBP = DBP- cDBP) was 33 cc / 100 g, Di / 2 was 34 nm, Dm0d was 58 nm, Di / 2 / Dmod was 0.59, and the ASTM aggregate volume was 106,129 nm3. It is a well-known fact that the aggregate diameter has a great influence on the characteristics of rubber, especially the tire rubber composition which is required to have great abrasion resistance. Therefore, the more concentrated the particle size distribution, the more popular it is. For example, Japanese Patent Laid-Open No. 6-1 7 9 7 7 4 discloses a carbon black obtained by separating the carbon black powder produced, whose "0/0 ^ is 0.36, 0.40, 0.47, 0.63. As above In the carbon black characteristics described above, two factors, such as particle size and aggregates, are taken as important conditions. However, in the above-mentioned Japanese Unexamined Patent Publication No. 6-1 79774, in order to obtain carbon black with a relatively concentrated aggregate diameter distribution, it is necessary to change The produced carbon black powder is processed by a very complicated method such as centrifugal separator. Therefore, "there are limits to the improvement of the carbon black production process", "ADso / Ds t (and Di / z / Dm〇d synonymous) 値 is 0. 6 The left paper size is applicable to China Standard (CNS) A4 specification (210X297 mm): 1〇: (Please read the precautions on the back before filling this page)

Λ A7 B7_ 5. Description of the invention 6). Right ". In this way, although the effect of carbon black with a narrow aggregate diameter distribution on the physical properties of rubber can be roughly understood, it is extremely difficult to obtain the expected aggregate diameter distribution. In addition, the particle diameter of carbon black,- A method of simultaneously controlling a plurality of important physical properties such as a cluster-group diameter and a cluster-body diameter distribution to a desired range cannot be achieved by a currently known method. In addition, when a diluent or a resin is added to an ink or a paint, the smaller the particle size and the smaller the aggregate, the smaller the dispersibility or fluidity. Among them, the relationship between the characteristics of carbon black and the characteristics of resins is generally unable to meet the requirements of both blackness and dispersion because there is no proportional relationship. Others, such as how to efficiently produce carbon black, are also one of the goals, especially the furnace method, which has excellent production efficiency, is equivalent to the blackness of pipes or more, and has good dispersibility when added to coatings or resins, and does not have Method for producing carbon black with the above disadvantages. Among them, the unreacted polycyclic aromatic hydrocarbons remaining in carbon black have often been accused of causing cancer in recent years. Therefore, the content of carbon black in the finished product and its safety in the finished product have become the focus of consideration. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Therefore, what is currently expected is a furnace method with excellent production efficiency, which is equivalent to the blackness of the pipe method, and added to Coating or resin can have good dispersibility, and a method for producing safe carbon black with low proportion of unreacted polycyclic aromatic hydrocarbons in the product. As described above, the relationship between the characteristics of carbon black and the physical properties of carbon black-containing components such as resin compositions is to meet the requirements of blackness, dispersibility, and safety that have opposite relationships to each other. In addition, it must have the Chinese paper standard (CNS) A4 (210X297 mm) as the paper size. ΤλΤΤ 536551 A7 B7 1. Description of the invention) Excellent abrasion resistance when added to the rubber component of the rubber composition, as a resin The composition can achieve the goal of suppressing deterioration. In addition, once the carbon black is dispersed, it must not be re-aggregated. … The present invention is to produce various kinds of carbon-containing hemp-hemp, in order to provide a carbon black filled with ® blackness, which can maintain excellent dispersibility and prevent aggregation, which is an object of the present invention. In addition, unreacted polycyclic aromatic hydrocarbons remaining in carbon black have often been accused of cancer risk in recent years. Therefore, the content of carbon black in products and its safety in finished products have become the focus of general consideration. Therefore, what is currently expected is a furnace method with excellent production efficiency, which is equivalent to the blackness of the pipe method, and has good dispersibility when added to coatings or resins, and contains a lower proportion of unreacted polycyclic aromatics in the product. Method for producing safe carbon black of hydrocarbon. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economics Therefore, the present invention aims to provide a method for producing carbon black which can satisfy both the characteristics of high blackness and excellent dispersibility. Yet another aspect of the present invention provides a method for producing carbon black, which can effectively produce primary plant aggregates with smaller diameters, smaller aggregate diameters, smaller aggregate distribution, and smaller aggregate diameters. In addition, in the production of various carbon-containing compositions, the present invention also aims to provide a carbon black having high blackness, which can maintain excellent dispersibility and prevent aggregation. In addition, in the production of various carbon-containing compositions, the present invention also aims to provide a carbon black which has high blackness, can maintain excellent dispersibility and prevent aggregation, and has high safety. As mentioned above, the production method of carbon black with a small particle size and high blackness, the results of the present inventors' knowledge, show that the high temperature heat content of hydrocarbon feedstock -12- (Please read the precautions on the back first Please fill in this page again} This paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) 536551 A7 ___B7____ V. Description of the invention (10) Dissolution and high flow rate of crude oil introduction position are important factors in the manufacturing method Among them, the physical conditions for the high flow rate of the crude oil introduction position, when it is actually used in a carbon black manufacturing furnace, even if a large energy supply device T is used to improve the characteristics, it has no excellent effect, that is, ... Investment and effectiveness-the results are not in equal proportions, which is a cause of confusion. In addition, increasing the temperature of the feed oil injection zone should be a method that can effectively produce small particle size and high blackness carbon black. However, in the past, the highest temperature part of the carbon black manufacturing furnace was made of alumina (high alumina or ultra high alumina) bricks. If the high temperature airflow in contact with it exceeds the refractory temperature (about 190) 0 t), After a short time of contact, problems such as spalling and dissolution will occur, and operation problems will occur. However, long-term operation under the conventional operating conditions that have not reached the refractory temperature will cause problems such as insufficient mechanical strength for wear resistance. Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards. For example, conventionally used zirconia refractories as ultra-high temperature refractories. Although zirconia has a high melting point of 2700 ° C and can withstand extremely high temperatures, but because of its high temperature gas phase It is extremely weak and has a large thermal expansion rate, which is a great problem in construction technology. Therefore, if it is used in a carbon black furnace, it lacks the necessary characteristics such as peel resistance and heat resistance, so the furnace is extremely damaged and difficult to put into practice. On the issue of chromium oxide refractory, some people have proposed to add additives to the chromium oxide refractory to improve its characteristics (Japanese Patent Publication No. 5 7 — 2 3 6 7 3, Japanese Patent Laid-Open No. 4 1 0 3 6 7 0 Announcement), but the inventors have found that long-term operation will cause the additives to scatter and reduce the heat resistance, and thus cannot maintain the characteristics necessary for a carbon black furnace for a long time. Read the notes on the reverse side and fill in this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7_ V. Description of the invention (11) Others, for example, the furnace body is forced to cool to make it resistant High temperature structure proposal (Japanese Unexamined Patent Publication No. 4-359068), but this structure will cause a huge burden on economy or operation when the furnace body is constructed or repaired, and it will be impossible to avoid the heat generated by cooling. Loss, but it is difficult to implement-the inventors have made in-depth research on the factors that can affect the dispersion behavior and blackness in the carbon black matrix, in order to make higher blackness and good dispersion than before. Carbon black is the goal of research. In particular, there are various methods for producing carbon black that has the same or better blackness as pipe black and has good dispersibility by the furnace method. As a result, it was learned that fine aggregates have a bad influence on dispersibility and large aggregates have a bad influence on blackness. Therefore, carbon black with fine aggregates without fine aggregates or large aggregates can have high blackness and Excellent dispersion. That is, carbon black with small particle size and small aggregate diameter in the aggregate diameter distribution is more concentrated. If there is no carbon black with large aggregate diameter, it is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read first Note on the back, please fill out this page again), you can get high blackness and better dispersion, so it can solve the problem that the blackness and dispersion cannot coexist. Therefore, Sai Ming has demonstrated that a novel carbon black with a Dmod of 80 nm or less and a Di / 2 / DmOd ratio of 0.6 or less can be directly prepared by a furnace method, and the obtained carbon black has excellent characteristics. In addition, the present inventors also found that, for example, the dispersibility of carbon black is affected by P 以外 in addition to the particle size and aggregate diameter. That is, if p Η 値 is low, it will cause a large amount of resin decomposition when mixed with the resin. Therefore, when it is used as a water-based coating, it will easily cause aggregation. If the ρ Η 値 of carbon black is set to a certain range, Will affect dispersion. That is, the first invention of this case is: a carbon black, which is characterized in that the average paper size is applicable to the Chinese Standard (CNS) A4 specification (210 × 297 mm) -14-'536551 A7 __B7 V. Description of the invention (12 ) Particle diameter is 13 nm or less, Dmd is 80 nm or less, D1 / 2 / Dmod ratio is 0. 6 or less, and pH 値 is 5 or more. And a resin composition, a rubber composition, a coating composition, and an ink composition? Characterized by containing this carbon black. The inventors also invented a novel carbon that can be directly prepared by the new furnace method. N2SA is more than 200 m2 / g, Dmod is less than 80 nm, and D i / 2 / Dmod ratio is less than 0.6. It is black and has been found to have extremely good characteristics. In addition, the second invention of the present case is: a carbon black, which is characterized in that N2SA is more than 200 m2 / g, DmOd is 80 nm or less, and the D i / 2 / Dm0d ratio is 0.6 or less, And pH 値 is 5 or more. And a resin composition, a rubber composition, a coating composition, and an ink composition containing the carbon black. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The inventors have made many researches on the method of solving the black pipe defects and the manufacturing method of the furnace method. As a result, it was found that if the ratio of the N2SA / S EM ratio to the surface area does not reach a certain value, the proportion of unreacted polycyclic aromatic hydrocarbons remaining in the carbon black cannot be ignored. Polycyclic aromatic hydrocarbons have often been accused of the risk of cancer in recent years. Therefore, if the content of carbon black in products is suppressed, the products can be made safer. The ratio of the specific surface area of N 2 SA / SE M is the ratio of the area of fine pores on the surface of carbon black. Therefore, if a specific surface treatment such as polymerizing the polymer on the surface of carbon black and grafting the coating polymer is used, It can increase the grafting rate and increase the proportion of surface treatment. When a conductive block is used, the conductivity can be improved. Others, such as the use of platinum or other metals as the catalyst carrier, can make the catalyst particle size smaller and easier to generate activity. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 77 ^ 1 " — 536551 A7 B7 V. Description of the invention (13). That is, the inventor found that he wanted to obtain high blackness and high dispersion When the carbon black with high safety and other desired physical properties is used, the pH / or the ratio of the specific surface area of SA / SE Μ should be set within a certain range. Then, these pH 値, N2SA〆-S Ε Μ When the specific surface area ratio 値 is set within a certain range, it has important effects such as maintaining high abrasion resistance when used as a rubber composition, preventing deterioration of the resin composition, and preventing aggregation when used as an aqueous coating. Therefore, by controlling these factors, carbon black can be efficiently produced. Therefore, the inventors have deliberately researched the results, and successfully found a carbon black with an average particle size of 13 nm or less, a specific surface area ratio of N2SA / S EM greater than 1.3, and a pH of 5 or higher. This carbon black also has very good characteristics. In addition, the present inventors have succeeded in researching a carbon black having an average particle diameter, a specific surface area ratio of N2SA / SEM, and a pH of a certain range, and this carbon black can also exhibit excellent characteristics. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). The third invention in this case is: a carbon black, which is characterized by an average particle size of 13 nm or less, N The ratio of 2 S A_7 S EM specific surface area is 1.3 or more, and pH 値 is 5 or more. And coating composition, resin composition, rubber composition, and ink composition containing this carbon black. In addition, the fourth invention of the present case is: a carbon black characterized by an average particle diameter of 14 nm or less, a ratio of N2SA / S EM specific surface area of 1.3 or more, a pH value of 5 or more, and a cDBP of 50 cc / 100 g or more. And a coating composition, a resin composition, a rubber composition, and an ink composition containing the carbon black. The above-mentioned Special Publication No. 5 4-7 6 3 2 states that although the paper size ^ applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm). 536551 A7 £ 7_ 5. Description of the invention (14). BET ratio Carbon black with a surface area / EM specific surface area ratio of 1.3 or less, but there is no record of the advantages when the ratio of BET specific surface area / EM specific surface area is a certain value or more, and other particle sizes can be controlled: £ P Η 値, or the size or distribution of aggregates ... c DBP and the effects of its dispersion-diffusion or blackness are not recorded at all. The present inventors conducted various reviews on the carbon black that had high blackness and good dispersion in the past. As a result, they found that it is not only necessary to control the diameter of the aggregates and the distribution of the aggregates, but also the type of the aggregates. That is to say, the developed state of the degree of dispersion is controlled in two ways to obtain carbon black with both blackness and dispersibility. Among them, the inventors paid great attention to the ratio DBP / D ^ d 値, which indicates the degree of development of the aggregates, and Dm0d, which indicates the size of the aggregates, and found that if this 値 is controlled to a certain value or more, A carbon black with high blackness and good dispersibility can be obtained. The inventors have also discovered that if the D B P / 0 ^ 値 of the small aggregate diameter is limited to a certain range or more, properties such as higher blackness and excellent dispersibility can be obtained compared with the conventional carbon black. ~ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) DBP / Dm〇d ratio 〇 If it is limited to a certain level or more, it shows aggregation when compared with the aggregate diameter The volume of the void portion of the body is large, so it is speculated that the type of the aggregate will be closer to a linear shape. This may be the reason why two opposite properties of blackness and dispersion coexist. Others, such as understanding that fine aggregates have an adverse effect on dispersibility, and large aggregates have an adverse effect on blackness, the inventors have invented carbon without uniform aggregates or large aggregates with uniform aggregates Black, developed in the past without the idea of coexistence. It has high blackness and excellent paper size. Applicable to China National Standard (CNS) A4 (210X297 mm) Γΐ7- 536551 A7 _B7_ V. Description of the invention (15) Good dispersion characteristics. That is, a novel carbon black with DmodM below 80nm, preferably • maintained below 40nm, with a DBP / Dmod ratio of 3.6 or more. It is preferable that the ratio of Dm0d equivalent to the maximum frequency Stokes equivalent particle size of the carbon black to the maximum frequency Stokes · Preferential particle size is half the ratio 値, that is, the ratio of Di / 2 / Dmod 値It is preferably 0.6 or less, and more preferably 0.5 or less. In order to obtain a high degree of blackness, the average particle diameter is preferably 13 nm or less. Carbon black produced in this direction also has characteristics. Therefore, the present invention provides a novel carbon black having a thickness of 80 nm or less, preferably 40 nm or less, and a D B P / Dm0d ratio of 3.4 or more. It is preferable to provide a ratio of the maximum frequency Stox equivalent particle size of Dm0d to the maximum frequency Stox equivalent particle size of a half width 値, that is, the ratio D1 / 2 / Dmod 値 is less than 0.6, More preferably, the novel carbon black is 0.55 or less. In order to obtain a high degree of blackness, the average particle diameter is preferably 13 nm or less, and carbon black produced in this direction also has characteristics. In the above-mentioned Japanese Patent Publication No. 5 4-7 6 3 2, although it is described that the average particle diameters of EM are 14 nm and 9 nm, carbon black with small particle diameters is small, but the size of the aggregates is an important factor for the particle size and blackness. Nothing is recorded, so the printing by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs shows that the present invention is novel and not inferable by current technology. That is, the fifth invention in this case is: a carbon black, which is characterized by: DBP / Dmcd is 3-4 or more, and Dmod is 80 nm or less. And a coating composition, a resin composition, a rubber composition, and an ink composition characterized by containing this carbon black. As explained above, the inventors have taken the -18- in the carbon black matrix (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297) ) 536551 A7 B7 V. Description of the invention (16) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The factors of dispersion and blackness are analyzed and compared with the previous technology Various studies were conducted with the goal of obtaining carbon black with higher blackness and excellent dispersion. As a result, it was learned that fine aggregates have a significant effect on dispersibility, and large aggregates have an adverse effect on blackness. Under the circumstances, the carbon blacks with fine aggregates or fine aggregates invented by the present invention have characteristics of high blackness and excellent dispersibility. That is, carbon black with small particle diameters and small aggregate diameters is extremely concentrated and there is no large aggregate diameter. Carbon black has high blackness and excellent dispersibility, that is, it has been invented to solve the above-mentioned blackness and dispersion. The method of obtaining the law and further research to obtain carbon black with this excellent characteristic more efficiently. As a result, the following objects were achieved and the sixth to eighth inventions of the present invention. First, in a manufacturing furnace having a specific choke tube section, a position where a hydrocarbon raw material is introduced is taken as a specific condition, so that the above-mentioned carbon black having excellent characteristics can be efficiently produced, thus completing the sixth invention of the present case. It is very unexpected to find that if a manufacturing furnace with a choke tube section with a specific length or more is used, and the oxygen concentration at the introduction position of the hydrocarbon raw material is minimized, a uniform aggregate diameter composed of a small particle diameter with excellent yield is obtained, and large particles are made. Carbon black with suppressed aggregates. That is, the sixth invention of the present case is the use of the first reaction zone region formed by the high-temperature combustion gas flow and the second reaction zone region having the gas barrier tube portion by mixing the obtained high-temperature combustion gas stream and the hydrocarbon raw material to generate carbon black. And, in a method for manufacturing carbon black in a manufacturing furnace constructed in a third reaction zone region downstream of the second reaction zone region to stop the reaction, the gas choke tube length is 80 mm or more, and the combustion gas at the introduction site of the hydrocarbon raw material A carbon black manufacturing method characterized by a middle oxygen concentration of 3vo 1% or less. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297mm) Γΐ〇. 536551 A7 B7 V. Description of the invention (17) Secondly, a carbon black manufacturing furnace with a specific choke tube is used to burn the gas inside the choke tube. When the gas flow rate is set within a certain range, carbon black having the above-mentioned excellent properties can be efficiently produced, and the present invention has been achieved. That is, the seventh invention of the present invention is to make · throw · by a high-temperature combustion gas-flow A first reaction zone region and a second reaction zone region having a choke tube section that mixes the obtained high-temperature combustion gas stream with a hydrocarbon raw material to generate carbon black and a third reaction zone region downstream of the second reaction zone region to stop the reaction In the method of manufacturing a carbon black manufacturing furnace, the carbon is characterized in that the length of the choke tube is 800 mm or more, the diameter of the choke tube part is 170 mm or less, and the flow velocity of the combustion gas in the choke tube is 2 500 m / s or more. Black manufacturing method. In addition, after understanding the following facts, it reached the eighth invention of the case. First of all, in order to achieve the purpose of reducing the primary particle size, after the introduction of the hydrocarbon raw material, the droplet diameter of the hydrocarbon raw material in the combustion gas in the manufacturing furnace will be reduced to a minimum to achieve the effect. Secondly, after studying the control of primary particle size and aggregate diameter, it was found that in order to produce carbon black with small particle size and small aggregate diameter, it must be printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. (Please read the precautions on the back before filling in this page.) To shorten the carbonization period of carbon black, it is necessary to generate carbon black within a very short period of time. Therefore, liquid hydrocarbon raw materials must be injected into the combustion gas to make the liquid The time for the raw material to evaporate is shortened, and the time for carbon black precursors and carbon black to be produced must be shortened, and after the introduction of the hydrocarbon raw material into the hot air stream, its surroundings must also be able to efficiently absorb the heat energy of the hot air stream. The inventors also apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) to the paper size of the droplet diameter of the hydrocarbon raw materials mentioned above to this paper size. -20-536551 A7 B7 V. Description of the invention ( 18) Various research results have been made on the conditions of dropletization and the conditions for shortening the reaction time of carbon black to make the energy of the surrounding hot gas more efficiently applied. In a specific state, Λ can achieve the above purpose. ...-That is, the eighth invention of the present case is the second gas barrier tube portion having a first reaction zone region formed by a high-temperature combustion gas flow and a carbon black mixed with the obtained high-temperature combustion gas flow and a hydrocarbon raw material. In the method for producing carbon black in a manufacturing furnace constituted by a reaction furnace zone and a third reaction zone region downstream of the second reaction zone region to stop the reaction, the mixing speed of the hydrocarbon raw material introduction site is 1 2 0 / The carbon black manufacturing method characterized by s or more is within the range specified in the sixth to eighth manufacturing methods of the present invention, and carbon black having various physical properties can be manufactured by changing conditions such as the amount of hydrocarbon raw material to be inserted. And can be used for various uses of various types of carbon black for arbitrary and efficient production. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The first invention in this case will be explained below. The carbon black of the first invention has an average particle diameter of 13 nm or less. The optimal range is 8 to 12 nm. If the average particle diameter exceeds 1 3 nm, the blackness of the coating will be insufficient if the coating is made. The term "average particle diameter" refers to the average particle diameter of the particle diameter obtained by an electron microscope method. Secondly, in the present invention, DmOd is 80 nm or less, and the ratio Di / 2 / Dm0d is 以下 or less, and preferably 0.5 or less. Among them, the ratio of D i / 2 / Dmc ^ d is the maximum frequency Stokes equivalent particle size Dmod obtained by the centrifugal sedimentation method, and the maximum frequency Stoke • 21 · (Please read the first Note: Please fill in this page again.) This paper size is applicable to China National Standard (CNS) A4 (210X297). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 536551 A7 B7 V. Description of the invention (19) The ratio of half to 値. It can also produce carbon black with a ratio 値 of 0.6 or less, more preferably 0. 55 or less, or a ratio of 75% by volume diameter D75 to Dmcd 値 D 7 5 / Dmod is 1 · 6 or less, more preferably 1 · Carbon black below 3. It can effectively suppress the content of large aggregate diameter substances that have an adverse effect on dispersibility that exceeds the body 4 * 75% diameter. That is, it is possible to efficiently obtain small-particle-size, small-aggregate-aggregate-aggregate-diameter distributions, and very large carbon-agglomerated-material-less carbon black. When the particle diameter, the aggregate diameter, and the aggregate distribution are set in a specific range as described above, the blackness and dispersibility can be satisfied at the same time, and excellent characteristics can be exhibited. That is, the carbon black of the present invention is a substance having extremely excellent blackness and improving dispersibility in various diluents. The carbon black of the present invention has properties of p H 値 5 or higher. When p Η 値 is less than 5, the resin composition using this carbon black is extremely susceptible to deterioration, and the rubber composition using this carbon black also deteriorates the abrasion resistance. Other water-based coatings made using this carbon black also have There is a problem that carbon black tends to accumulate. Therefore, the preferred ρ Η 値 is 6 or more. The method for measuring P 一般 is generally the method described in J ISK6221- 1 982. Pipe blacks that are currently sold on the market for small black carbon blacks with excellent blackness are generally known to be ρ ρ 5 or less, and usually 3 or less. The carbon black of the first invention of the present invention described above is a novel and extremely useful substance, and can be produced by a simple manufacturing method described later. The carbon black of the first invention of this case is that when the particle diameter, Dmod, Di / 2 / Dmod ratio 値 and ρ 说明 described above are controlled in a specific range, the blackness and dispersion that could not coexist in the past can be Sexual relationship is satisfied. This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -22: ---------------. Order ------ Φ-- (Please read the back first (Notes on this page, please fill out this page) 536551 A7 B7 V. Detailed description of the invention).

cDBP is preferably at least 50cc / 100g. cDBP can also be referred to as broken DBP absorption coefficient, and is measured in accordance with ASTM D -349 3-88. When the cDBP is less than 50 c / 100g, the dispersibility is not good. The best of cDB-P-zhi is 6 0 c_c / 100 g or more. The second invention will be described below. Among the carbon blacks of the fourth invention, the nitrogen adsorption specific surface area (N2SA) was first 200 m2 / g or more. It is preferably at least 400 m2 / g, and more preferably at least 500 m2 / g. When N2SA is less than 200 m2 / g, the blackness and degree of the paint when it is formed are sufficient. Secondly, in the second invention of the present invention, Dmod is 80 nm or less, and the ratio D 1/2 / Dmod 値 is 0.6 or less, and preferably 0.5 or less. Dm 0d is preferably 20 to 80 nm or less. Such a carbon black with a small aggregate diameter exhibits remarkable blackness when used as a colorant, and also has excellent physical properties when used as a rubber composition. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page), where the ratio D i / 2 / Dn ^ d is the maximum frequency delay obtained by the centrifugal sedimentation method The ratio of the Dmod of the equivalent particle size to the half frequency of the maximum frequency Stoker equivalent particle size is 値. In addition, the ratio 値 is less than 0.6, more preferably, the ratio of volume 7 5% diameter to Dmod 値 D 7 5 / Dm〇d is 1.  Carbon black of 6 or less, more preferably 1.3 or less. It can effectively suppress the content of large aggregate diameter substances that have an adverse effect on dispersibility in excess of 7 5% by volume. That is, it is possible to efficiently obtain small-particle-size, small-aggregate-aggregate-aggregate-diameter distributions, and extremely large aggregate-diameter materials with very little carbon black. In this way, the specific surface area, aggregate diameter and aggregate distribution are set on a paper scale. Applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 23- 536551 A7 ΒΊ _______ 5. Specific scope of the invention (21) At the same time, it can meet the blackness and dispersibility at the same time and can exert excellent characteristics. That is, the carbon black of the present invention is a substance having extremely excellent blackness and dispersibility higher than that of various diluents. … And the second invention of the carbon black in this case has a property of 4 Η 値 5 or more. When P Η 値 is less than 5, the resin composition using this carbon black is extremely easy to degrade 'and the rubber composition using this carbon black will also deteriorate the abrasion resistance, and other water-based coatings made using this carbon black will also deteriorate. There is a problem that carbon black tends to accumulate. Therefore, the preferred ρ Η 値 is 6 or more. The method for measuring ρ Η 値 is as described above. The third invention of this case will be described below. In the carbon black of the third invention, first, it is a substance having an average particle diameter of less than 13 nm. More preferably, it is 8 to 12 nm. When the particle diameter is 1 3 nm or more, the blackness is insufficient when used as a paint. The average particle diameter is an average particle diameter obtained by an electron microscope method. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The third invention of the carbon black in this case has an N2SA / S EM specific surface area ratio of 1.3 or more. If this ratio is less than 1.  At 3, problems such as difficulty in oxidation treatment occur. And this ratio 値 is related to the proportion of unreacted polycyclic aromatic hydrocarbons remaining in carbon black, if this ratio 値 is less than 1.  At 3 o'clock, the content of polycyclic aromatic hydrocarbons will cause safety issues that cannot be ignored. When it is larger than 1 · 3, it is preferably 1 · 5 or more, and more preferably 1 · 8 or more. However, if the ratio is too large, the viscosity at the time of manufacturing the ink composition will increase, which will adversely affect the dispersibility. So generally it is 2. 8 or less, preferably 2.  5 or less is appropriate. The carbon black of the third invention in this case has a pH value of 5 or higher, and the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 24- 536551 A7 __B7___ 5. The description of the invention Bismuth) Less than 5 At this time, the resin composition using this carbon black is extremely susceptible to deterioration, and the rubber composition using this carbon black also deteriorates the abrasion resistance. Other water-based coatings made using this carbon black can also cause carbon black to easily aggregate. Wait for the question. Therefore, the preferred pH value is 6 or more. The method for measuring the pH 値 ϋ 2 S A / S Ε M ratio is as described above. When the carbon black of the third invention of the present case is set as above, the particle size, the specific surface area of N2 SA / S EM, and ρ 于 can be set to a specific range, which can satisfy both the blackness and the dispersibility, and can exert extreme effects. Excellent characteristics. The aggregate diameter of the third invention of the present case is not particularly limited, and it is preferable that Dm0d is 80 nm or less, and more preferably 40 nm or less. The effect of the aggregate diameter on the dispersibility and blackness as described above will gradually become clear. In the present invention, for carbon black adjusted to a specific particle size, N2SA / S EM specific surface area, and pH 値, if Dmd When it is set to 80 nm or less, and more preferably 40 nm or less, a specific and excellent effect will be exhibited. In this way, when the particle diameter and the aggregate diameter are set in a specific range, the blackness and dispersibility can be satisfied at the same time, and excellent characteristics can be exhibited. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page), where the ratio D i / 2 / Dn ^ d 値 is below 0.6, preferably below 0.5 5 5 In addition to excellent blackness, higher dispersion can be obtained. Among them, the ratio of Di / 2 / D ^ d is the ratio of half the width of the maximum frequency Stokes equivalent particle size Dmod obtained by the centrifugal precipitation method to the maximum frequency of Stokes equivalent particle size. value. In addition, the ratio 値 is less than or equal to 0.6, and more preferably, the ratio of the diameter of 75% by volume to Dm0d is 7D 7 5 / 0_ is 1.  Carbon black below 6. It can effectively restrain the paper size which has a bad influence on the dispersion. The Chinese national standard (CNS) A4 specification (210X297 mm) is applicable. 25 · 536551 A7 _B7_ V. Description of the invention Pan 3) (Please read the note on the back first) Please fill in this page again for the contents) Content of large aggregate diameter material with 7 5% diameter. That is, it is possible to efficiently obtain small-particle-size, small-aggregate-aggregate aggregate-diameter distributions, and extremely large aggregate-diameter substances with very little carbon black. In addition, the inventors also found that in order to obtain a high blackness for this carbon I, Dn ^ d is preferably 20 to 8 η ·· ιη ··, c DBP is preferably 54) cc / 1 00g or less, This carbon black was also successfully produced. The cDBP is preferably 50 cc / 100 g or more. cDBP is also called the broken DBP absorption number, and it is measured according to ASTM D-3493-88. When cDBP is less than 50cc / 100g, the dispersibility is not good. The best of cDBP is 60cc / 100 g. Next, a description will be given of the fourth invention in this case. In the carbon black of the fourth invention, first, it is a substance having an average particle diameter of 14 nm or less. It is more preferably 8 to 12 nm. When the particle size exceeds 14 nm, the blackness is insufficient when the coating is used as a coating. The average particle diameter is an average particle diameter obtained by an electron microscope method. In the carbon black of the present invention, the ratio of the specific surface area of N2S A ^ / S EM is printed on the consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs for more than 1.3. This ratio 値 is related to the proportion of unreacted polycyclic aromatic hydrocarbons remaining in carbon black. If the ratio 大于 is greater than 1.3, the content of polycyclic aromatic hydrocarbons can be greatly reduced. From a safety point of view, Better way. In the fourth invention of this case, the ratio of N2SA / SEM specific surface area is 1.3 or more, preferably 1.5 or more, and more preferably 1.8 or more. When the ratio is too large, the viscosity at the time of manufacturing the ink composition is increased, and the dispersibility is adversely affected. Therefore, it is generally below 2 · 8, preferably below 2 · 5. The size of this paper applies Chinese National Standard (CNS) A4 (210X297 mm) -26-536551 A7 B7 __ ^^ V. Description of the invention Bismuth) The ratio of N 2 SA / SE Μ specific surface area is obtained separately first The specific surface area of Α and S Ε M is obtained by calculating the specific surface area. The measurement of N2SA is performed according to ASTM 0-3037-8 ^. The measurement method of the specific surface area of S E M is calculated by the following formula. SEM = 6000 / (p-dA) P = Specific gravity of carbon black (1 · 86g / cm3) d A = (Particle) volume area diameter (nm) And the carbon black of the fourth invention of this case has a pH 値 of 5 or more, When the pH is less than 5, the resin composition using this carbon black is extremely susceptible to deterioration, and the rubber composition using this carbon black will also deteriorate the abrasion resistance. Other water-based coatings made using this carbon black will also deteriorate. Carbon black is liable to accumulate. Therefore, the best p Η 値 is 6 or more. The method for measuring p 如 is the same as described above. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) In the fourth invention of this case, cDgP is preferably 50cc / 100g or more. cDBP is also called broken DBP absorption number, and it is measured according to ASTM D-3493-88. When cDBP is less than 50cc / 100g, the dispersibility is not good. The best of cDBP is 60 c c / 1 OOg. The carbon black of the fourth invention of the present case, when the particle size, the ratio of N2SA / SEM specific surface area 値, pH 値, and cDBP are set in a specific range as described above, can satisfy both the blackness and dispersibility, and Can exert excellent security. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-27: 536551 A7 B7 V. Description of the invention (25) · There is no special limitation on the aggregate diameter in the fourth invention of this case. The preferred Dr ^ d is 80 nm or less, and more preferably 40 nm or less. The effect of the aggregate diameter on the dispersibility and blackness as described above will gradually become clear. In the present invention, the specific surface area adjusted to a specific particle size and the specific surface area of N 2 SA / -SE Μ For carbon blacks at specific ratios, specific P Η 値 and specific c D Β P, if Dd is set to 8 η m or less, and more preferably 4 η η m or less, a specific and excellent effect will be exhibited. A better situation is to adjust the ratio Dmu of the maximum frequency Stox equivalent particle size to the maximum frequency Stox equivalent particle size 値 D] / 2 ratio D i / 2 / Dmod to be adjusted to 0.6 or less, When it is preferably 0.5 or less, excellent blackness and excellent dispersibility can be obtained. In the scope of the present invention, the volume ratio of D75 to Dmd is 75% by volume, and D 7 5 / D ^ d is 1.6 or less, preferably 1.6 or less, and more preferably, it is a consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Printed (Please read the precautions on the back before filling out this page) Carbon black below 1 · 3. It can effectively suppress the content of large aggregate diameter substances that have an adverse effect on dispersibility in excess of 7 5% by volume. That is, in the present invention, the average carbon particle diameter is 13 nm or less, and the ratio of the specific surface area of N 2 S A / S E M is greater than 1.3. The pH is 5 or more carbon black. That is, a coating composition, a resin composition, a rubber composition, and an ink composition containing this carbon black are characteristic. Hereinafter, in the carbon black of the fifth invention of the present case, DB P / Dm0d is 3.4 or more, Dmod is 80 nm or less, and more preferably 4 Onm or less. When D B P / Dd is less than 3.4, dispersibility is poor when used as a black pigment, and if Dmod exceeds this range, the blackness is also insufficient. In addition, the paper size of the maximum frequency Stox equivalent particle size half of the maximum frequency obtained by the centrifugal sedimentation method modD and the maximum frequency Stox equivalent particle size Dmod are applicable to the Chinese paper standard (CNS) A4 specification (21 〇X297 mm) ~~ "28- " 536551 A7 B7 V. Description of the invention (26).  The ratio 値 D i / 2 / ratio 値 is 0 · 6 or less, and more preferably 0 · 55 or less. It is also possible to obtain a ratio of volume 7 5% diameter to Dmod 値 D 7 5 / Dn ^ d is 1 · 6 or less, preferably 1.  Carbon black below 3. This substance can effectively suppress the content of large aggregate diameter substances that have an adverse effect on dispersibility in excess of 7 5% by volume. That is, it is possible to efficiently obtain aggregates with small particle diameters and small aggregate diameters. The aggregate diameter distribution is extremely concentrated and the substances with large aggregate diameters have very little carbon black. In this way, when the aggregate diameter and the aggregate distribution and particle size are adjusted within a specific range, the blackness and dispersibility can be satisfied at the same time and excellent characteristics can be exhibited. That is, the carbon black of the present invention is an excellent carbon black and can improve the dispersibility of various diluents. The carbon black of the present invention has a pH value of 5 or higher, and when the pH value is less than 5, the resin composition using the carbon black is easily degraded, and the rubber composition using the carbon black also deteriorates the wear resistance. Others For example, water-based coatings prepared using this carbon black also cause problems such as easy aggregation of carbon black. Therefore, the best P Η 値 is 6 or more. The method for measuring p 如 is as described above. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). There are no restrictions on the manufacturing methods of the carbon blacks described in the first to fifth inventions in this case. The sixth or lower manufacturing method invention is a preferred manufacturing method. The sixth invention of this case is an invention of a so-called furnace method, which is a method of introducing a hydrocarbon raw material to produce carbon black in a manufacturing furnace having a first reaction zone region, a second reaction zone region, and a third reaction zone region. . The structure of the present invention will be described using drawings. Figure 1 is an important part of the legend of the carbon black manufacturing furnace that can be used in the present invention. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 cm) -29-536551 A7 B7 V. Description of the invention (27) Cross section槪 Sketch. A first reaction zone region 1 formed by a high-temperature combustion gas stream and a first reaction zone region 2 having a gas barrier tube portion formed by mixing the obtained high-temperature combustion gas stream and thorium carbide raw material to form carbon black are provided in the furnace length direction ( -Belongs to the choke tube part 4) and the third reaction zone region 3 located downstream of the second reaction zone region to stop the reaction. The process of each reaction zone itself can basically adopt the same treatment method as before. Combustion hydrocarbons and oxygen-containing gas are introduced into the first reaction zone area from the combustion nozzle 5 to generate a high-temperature airflow. The oxygen-containing gas is generally air, oxygen, or a mixture thereof, and the hydrocarbon raw materials are generally hydrogen-based, carbon monoxide, natural gas, petroleum gas and other petroleum-based liquid fuels such as heavy oil, and fossil-based liquid fuels such as phenol dye oil. In the second reaction zone, the high-temperature gas stream obtained in the first reaction zone is introduced into the hydrocarbon feedstock nozzle 6 in a cocurrent or lateral direction. The hydrocarbon feedstock is introduced in a spray manner, and the hydrocarbon feedstock is thermally decomposed into carbon black. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). Hydrocarbon raw materials are generally benzene; aromatic hydrocarbons such as toluene, xylene, naphthalene, anthracene, phenolic oil, and carboxylic acid oil Preferred are coal-based hydrocarbons, ethylene-based heavy oils, petroleum-based heavy oils such as ECC oil, acetylene-based partially saturated hydrocarbons, ethylene-based hydrocarbons, aliphatic saturated hydrocarbons such as pentane or hexane, and the like. The third reaction zone region cools the high-temperature reaction gas to 100 ° C to 800 ° C or lower, and sprays the cooling medium of liquid or gas such as water via the reaction stop fluid introduction nozzle 7. The cooled carbon black can be treated by a known general method such as separation and recovery of gas by using a trap filter, a mesh bag, or the like. In the figure, 8 is a control valve. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -30 · 536551 A7 B7 V. Description of the invention (28) In the present invention, the second reaction zone is a part with a gas blocking tube section, The tracheal part is a part where the cross section is rapidly reduced. In the present invention, the gas blocking tube portion is 800 nm or more, and preferably 800 to 3000 nm. ^ The inventors have found that the carbon black produced in this range can have a minimum aggregate diameter range. In the formation area of general aggregates, the present inventors have conducted in-depth review and found that it is better to avoid the change of the flow path and thus cause a highly disturbed field without having a narrow part. If the distribution of controlled aggregates is compared with the case of controlled particle size distributions, it can be seen that the former requires longer control time. Therefore, the choke tube part must have a certain length, so that the conditions of the primary particles of carbon black supplied to the hydrocarbon raw material and the reaction zone area until the aggregate is formed are the same, and the primary particles of the carbon black supplied to the hydrocarbon raw material and the generation of aggregation are suppressed. At the end of the generation reaction at the end of the body, the cross-sectional shape of the flow path changes greatly. The choke tube with the length described above can control the distribution of the aggregates, and has the effect of preventing the formation of large aggregates. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The entrance of the choke tube at the front end of the choke tube is the axis that contains the narrowest part of the flow path and the convection path is reduced In terms of direction, the change of 値 whose angle exceeds 5 ° is 5 ° or less. The outlet of the choke tube portion at the tip of the choke tube is a portion whose angle exceeds 5 ° in the axial direction in which the flow path is reduced. Further, in the seventh invention of the present case, the diameter of the choke tube portion is 1 70 mm or less, preferably 30 to 1 70 mm, and more preferably 50 to 150 mm. The present inventors have found that in this range, it is extremely easy to produce a substance having a small particle diameter and a small aggregate diameter and a highly concentrated aggregate diameter distribution. This paper size applies to China National Standard (CNS) A4 specification (210X297 cm). 31-536551 A7 B7 ___ V. Description of the invention (29) Furthermore, in the seventh invention of this case, the reason why the carbon black with good physical properties can be obtained through a small-diameter choke tube portion with a flow rate above a certain threshold and below a certain threshold should be Because the flow velocity of the combustion gas in the choke tube with a smaller diameter is kept constant, the turbulent mixing and mixing ratio of the gas in the choke tube can be increased, in addition to promoting the atomization of the hydrocarbon raw material droplets. It can generate the same environment as the carbon black generation reaction, so that the thermal energy of the combustion gas can be more effectively used by the carbon black generation reaction, thereby increasing the reaction speed and making the reaction environment the same, so carbon black can be generated in a short time and Carbonizing the carbon black results in a carbon black with a small particle size and a small aggregate diameter, which is more efficiently distributed. The faster the gas flow in the choke tube, the better. Generally, after the introduction of hydrocarbon raw materials, the combustion gas moves and thermal energy is used to atomize it. Therefore, the faster the combustion gas temperature is, the better, generally it is more than 250 m / s, and it is preferably 300 to 5 0 Om / s is better. In this range, carbon black with smaller aggregates and a narrower particle size distribution will be easily obtained with a small particle size. In particular, the combustion gas flow rate of the choke tube is above 250 m / s, which is the seventh invention of this case. Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives (please read the precautions on the back before filling out this page). After in-depth review, the inventor learned that in order to achieve the purpose of reducing the particle size of the primary particles of carbon black, It is effective to reduce the droplet diameter of the hydrocarbon raw material immediately after the hydrocarbon raw material is introduced into the combustion gas of the manufacturing furnace. In the production method of carbon black, the hydrocarbon raw materials are generally made into particles by using the motion and thermal energy of a high-speed combustion gas. However, this technology is still unable to achieve sufficient small particle size, so after a more in-depth review of the production of micronizers in high-speed airflow, we learned that the dropletization caused by the airflow is suitable for the paper size relative to the paper China National Standard (CNS) A4 specification (210X297 mm) -32- " " 536551 A7 B7 V. Description of the invention (30) Speed difference and time required for the particles sprayed in the airflow to accelerate to close to the airflow speed related. After reviewing the relationship between the final particle size of the hydrocarbon raw material and the gas flow, it is known that the faster the gas flow before the gas flow rate is 2 5 ^ 0-m / s, the faster the number of particles reaching the final particle size will be. Decreased, after more than 250 m / s its reduction speed slowed down. Therefore, the flow velocity of the gas introduced into the narrow part must be more than 250 m / s, and more preferably 50 Om / s or more. The present inventors have found that the introduction method of the hydrocarbon raw material in the narrow part is effective for the gas. It is better to approach the horizontal direction. As described above, when the flow velocity does not reach 250 m / s, it is extremely difficult to obtain the effect of sufficiently reducing the particle size for the purpose of the present invention. Among them, the eighth invention of the present case is characterized by setting the turbulent mixing intensity of the combustion gas flow at the introduction site of the hydrocarbon raw material to a specific range. In other words, the turbulent mixing speed of the combustion gas flow at the introduction site of the hydrocarbon raw material is set to 120 / s or more. With this setting, carbon black with a more concentrated aggregate distribution can be made more efficiently with a small particle size and small aggregate diameter. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Turbulent mixing speed is higher than this. In addition to promoting the atomization of hydrocarbon raw materials, it can also cause The environment of the black generation reaction is the same, so that the thermal energy of the combustion gas is more effectively used by the carbon black generation reaction, thereby increasing the reaction speed and making the reaction environment the same. Therefore, carbon black can be generated and carbonized in a short time. As a result, carbon black with a small particle diameter and a small aggregate diameter can be produced more efficiently with an extremely concentrated aggregate diameter distribution. Among them, this physical quantity called the turbulent mixing speed is obtained by introducing an index showing the turbulent mixing strength. This is the turbulent dissipation rate ε (m 2 / this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -33 · 536551 A7 B7 V. Description of the invention (31) ·.  (Please read the notes on the back before filling in this page) s 3) The physical quantity obtained by dividing the intensity of the turbulent energy k (m 2 / s 2) is used as the unit of turbulent mixing intensity in the unit of (1 / hour) An indicator. The ε and k are a theoretical quantity that generally represents the size of the turbulent flow in fluid mechanics. 6 and 1 ^ can also be calculated by a well-known method such as general numerical calculation. In the present invention, the turbulent flow mode in numerical calculation uses a general k-ε mode. The inventors have learned through many studies that the ε / k 値 of the gas flow at the introduction position of the hydrocarbon raw material has a considerable relationship with the quality of the produced carbon black. That is, if the turbulent mixing speed (ε / k) 导入 of the hydrocarbon feedstock introduction position is set to a certain range, carbon black having a small primary particle diameter and aggregate diameter and extremely concentrated aggregate diameter distribution can be generated. To increase ε / k 大, increasing the gas flow rate in the choke tube has its effect, and reducing the diameter of the choke tube can also increase ε / k 値. In addition, the angle of the narrowed part of the choke inlet is also very important. Ε / k 値 increases when the angle is sharper. Employees' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives So after in-depth research, the inventors finally explained how to effectively produce carbon black with small particle size, small aggregate diameter, and extremely concentrated aggregate diameter distribution. Therefore, a simulation test of various conditions is performed, and it is known that the ε / k 値 of the introduction position of the hydrocarbon raw material must be at least 120 / s, and 500 ~ 5000 / s is more preferable. The inventors have studied the results and found that in order to obtain a carbon black with a primary particle diameter and a large agglomeration diameter, the time required for the liquid hydrocarbon raw material to be sprayed to the combustion gas to evaporate must be shortened, and the carbon must be shortened. The generation time of black precursor and carbon black is better. In this way, the hydrocarbon material is introduced into the hot air flow. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) = 34-536551 A7 B7 V. Description of the invention (32).  Then, how to absorb the thermal energy of the surrounding hot airflow is extremely important. Therefore, the acquisition of ε / k 値 can shorten the time from carbon black generation to carbonization and generate carbon black in a very short time. As a result, carbon black with a smaller particle size and agglomerate diameter can be obtained in a short time. Therefore, it is presumed that if the droplet diameter of the hydrocarbon raw material is atomized and the thermal energy of the surrounding environment is effectively used, the time for the carbon black generation reaction can be shortened at the same time. The shape of the choke tube inlet is preferably a specific shape described below. That is, the choke tube inlet angle is 45 ° ~ 100 °, preferably 80 ° ~ 90 °, and most preferably 90 °. In addition, the angle of the choke tube inlet is the angle of the upper side of the airflow among the angle formed by the wall surface of the choke tube inlet convergent portion and the furnace shaft, that is, the angle corresponding to part 12 in FIG. 2. This 値 is between 45 ° and 90 °. The larger the 値 is, the larger the reduction of the cross-sectional area relative to the distance on the axis of the furnace facing the choke tube will be. When it is 90 °, it becomes a rapidly shrinking state. In addition, in FIG. 2, 9 is an inlet portion of the choke tube portion, 10 is a choke tube portion, 11 is a fuel gas flow direction, and 12 is an angle of the choke tube portion inlet. ~ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Also, if the inlet angle of the choke tube section is set according to certain conditions, regardless of the length of the choke tube section It is applicable, but it is preferable to set the choke tube part to 800 mm or more, and if the flow rate is 250 m / s or more, the multiplicative effect can be exhibited. Other inventors have found that, for example, when the inlet angle of the choke tube part is set to be 45 ° or more and 100 ° or less, preferably 80 ° or more and 90 ° or less, and most preferably 90 °, it can be easily obtained once. Carbon black with small particle size and aggregate diameter and extremely concentrated aggregate diameter distribution. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 cm): 35- 536551 A7 B7 V. Description of the invention (33) Generally, the airflow through the choke tube section with a specific inlet angle range is used to produce The reason for having good physical properties of carbon black should be that the combustion gas in the choke tube can maintain a high speed and the angle of the inlet i of the choke tube part has a large angle, which can increase the turbulence of the gas in the choke tube. In addition to promoting the dropletization of hydrocarbon raw materials, the same environment as the carbon black generation reaction is generated, so that the thermal energy of the combustion gas can be efficiently used by the carbon black generation reaction, thereby improving the reaction speed and the reaction status. It is homogenized, and carbon black can be generated and carbonized in a short time. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Generally, it takes a lot of time and labor to perform various experiments on the entrance angle of the choke tube department. The carbon black production steps are used to develop various simulation programs, and use this program to make various investigations on the angle of the entrance. This program is a commonly used thermal fluid analysis program using the differential phenol method and a program for generating carbon black primary particle size based on the classical nuclear generation theory developed by the inventors. Change the shape of the furnace or the operating conditions to test the prediction of various changes in the primary particle size or distribution of the carbon black produced. Specific examples such as "Aerosol Research Volume 12 No. 3 PP. 175 ~ 182 (1997) ". The sixth invention of the present case is characterized in that the oxygen concentration at the position where the hydrocarbon feedstock is introduced is set to 3 vo 1% or less. It is preferably 0. 5 to 1 v ο 1%. The present inventors have found that in this way, the obtained carbon black can have a small aggregate diameter and have an extremely concentrated aggregate distribution, and in addition, can suppress the generation of large particle size aggregates, and can enable the production of small particle size materials Relatively improved. This paper size applies to China National Standards (CNS) 8-4 specifications (210X297 mm) -36- 536551 A7 B7__ V. Description of the invention (34) The furnace black system obtained from the previous furnace removal is part of the hydrocarbon raw materials generated by combustion Based on the experience of the material, the remaining oxygen concentration in the combustion gas at the introduction site of the hydrocarbon raw material is 5 ~ 10vo1¾, so that a part of the raw oil is burned. The present inventors have discovered very unexpectedly that if the oxygen concentration is suppressed to a very small amount, the aggregate distribution will be more concentrated and there is no large particle size outside the aggregate, and the carbon black with small aggregate diameter and high yield will be produced. Way made. The reason for suppressing the oxygen concentration at the introduction site of the hydrocarbon raw material to achieve the purpose of the present invention is not well understood. The inventors conducted various tests on the oxygen concentration at this site and learned that the lower the The C 0 concentration will also decrease. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). The decrease in the concentration of C0 means that the proportion of C 0 2 generated by the combustion reaction will increase, and that produced by the combustion reaction will increase. When the heat is increased, it will cause the combustion gas to decline in high temperature. When the remaining gas forms C 0 2, the reaction formula is C + 〇2-C〇2, when CO forms, the reaction formula is 2 C + 〇2-2 CO, so from the reaction formula: when Γ solution is to form CO Requires 2 times more carbon atoms. Therefore, if the oxygen concentration at the introduction site of the hydrocarbon raw material is reduced, the production of C 0 will be reduced, so it is possible to obtain a small particle size carbon black and increase the yield. In addition, when the oxygen concentration at the introduction site of the hydrocarbon raw material is small, the combustion amount of a part of the hydrocarbon raw material can be reduced, and the environment of the carbon black generating region can be maintained at a certain condition. This point may be able to obtain extremely distributed aggregates. The reason for concentrated carbon black. The measurement of oxygen concentration at the introduction site of hydrocarbon raw materials is generally adopted. The paper size is applicable to Chinese National Standard (CNS) A4 (210 × 297 mm) -37-536551 A7 B7_. _ V. Description of the invention) Take the gas at the introduction site of the hydrocarbon raw materials, and then measure nitrogen, oxygen, carbon dioxide, carbon monoxide, hydrogen, methane, acetylene, etc. with a gas chromatography analyzer. Water from combustion is not included. ^ The introduction of hydrocarbon raw materials should be located in the choke tube, and ^ should be within a range of 1 m s from the choke tube inlet to the cross-section average flow velocity of the combustion gas. More preferably, it is 0. Fan Ye of 6ms. A carbon black having a small particle diameter and a uniform aggregate diameter can be produced when an introduction step is performed with this part. After the introduction of hydrocarbon raw materials, the residence time in the choke tube is 0.  Above 4ms is preferred. In this way, carbon black with extremely concentrated aggregate distribution can be easily produced. Aggregates may be substances formed by the thermal decomposition of hydrocarbon raw materials, condensing and condensing into droplets to form a precursor that forms a nucleus, and melting and carbonizing by collision with each other. Therefore, if the time staying in the choke tube is within the above range, aggregates can be generated without being affected by the high disturbance field caused by flow path changes and the like. * Here, in the present invention, after the hydrocarbon raw material is introduced into the device, it is preferable that it is not affected by the disordered state generated by the air flow for a certain period of time. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The specific content of the invention is "not affected by the disturbance caused by the air flow". In general fluid mechanics, "turbulence" refers to the magnitude of the turbulent energy (m 2 / s 2) and the vortex dissipation rate (m 2 / s 3). The inventors performed various experiments and applied simulations performed by fluid mechanics. The experiment, and the in-depth study of the relationship between various experimental conditions and their physical quantities, especially in order to prevent the formation of large aggregate diameter aggregates, after the introduction of raw oil (hydrocarbon raw materials) 1.  Within 5 ms, the turbulence energy and eddy current can be dissipated. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 38- 536551 A7 B7 V. Description of the invention (36) Any increase in the rate The rate is suppressed to below 10 ¾, which can substantially suppress the disturbance of the flow state of the airflow. This should be the reason that in the process of generating carbon black aggregates, it can actually inhibit the generation of aggregates with large aggregate diameters. -The situation of the turbulent flow energy change in the center of the flow path will be described in more detail using Figure 3 as an example. Due to the reduction of the cross-sectional area of the flow path at the entrance of the choke tube section, the turbulence energy shows a peak 値 (A), and then gradually decreases. After that, the peak of the choke outlet enlarged again (C). The aforementioned "When the feed oil (hydrocarbon raw material) is introduced within 1 · 5 ms, the increase rate of either the turbulent flow energy or the eddy current dissipation rate can be suppressed to less than 10%", which refers to the feed oil in Figure 3. The time from the point of introduction B to the point C where the turbulence energy increases remains above 1.5 ms, and the turbulence energy 値 D before the C point and the maximum 乱 E ratio 乱 E of the turbulence energy at the C point 値 E / D is 1.  1 or more. ~ Also, in this example, the turbulence energy before B to C is a simple reduction, but the present invention is not limited to the case where the simple reduction is made. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Please read the precautions on the back before filling out this page.) Under the conditions of the present invention, if the hydrocarbon raw materials are supplied until the carbon black primary particles and aggregates are formed, When the reaction conditions in the reaction zone area are kept uniform, after the supply of hydrocarbon raw materials to the end of the reaction to produce carbon black primary particles and aggregates, the cross-sectional shape of the flow path is greatly changed to prevent high disturbance. Therefore, carbon black with uniform aggregate diameter and no large aggregate diameter can be produced. That is, the carbon black aggregation system is formed by the thermal decomposition of hydrocarbon raw materials, condensed and condensed into droplets, forming a precursor of the nucleus and generating primary particles. After this paper size, the Chinese National Standard (CNS) A4 specification (210X297) 11 -39--536551 A7 B7_ V. Description of the invention (37) · A substance made of particles colliding with each other and melting with each other through carbonization. Therefore, the choke tube is longer and the area of aggregate formation is not. Those with high disturbance fields due to flow path changes, such as narrow areas, are preferred. The inventors have discovered that if the situation of controlling the distribution of aggregates and the situation of controlling particle size distribution 4 are compared, it is known that the former needs Longer time control. The present invention achieves the purpose of not disturbing the flow state of the gas flow within 1 · 5ms after the introduction of the hydrocarbon raw material.  If the shape of the flow path is greatly changed within 5 m s to cause disturbance, the generation of large aggregate diameter aggregates cannot be ignored, which will cause the uneven distribution of carbon black aggregates. As explained above, it is best that the flow state of the airflow is not disturbed during the production process. Therefore, the inner wall of the choke tube part is preferably as described below. That is, the inventors found that the diameter of the aggregate is also affected by the smoothness of the inner wall of the airway in addition to the length of the airway. Therefore, if the length of the airway is set to a specific value or more, the inner wall of the airway is smooth. When the degree is set to a specific value or less, a substance with extremely concentrated aggregate distribution and extremely excellent carbon black properties can be obtained. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The smoothness of the inner wall of the choke tube is preferably ε = 1 mm or less, and more preferably 0 · 3 mm or less. Here, ε is an index of the smoothness of the inner wall of the choke tube, and is generally referred to as the equivalent coarseness of sand. (Mechanical Engineering Fact Sheet New Version A.5. Fluid Mechanics Chapter 11 Flow in the Flow Path 11. 2 Tube friction coefficient of straight pipe). Among them, the equivalent sand particle thickness is defined as the coefficient of friction of the tube when measuring the flow in the tube. It refers to the definition of the thickness of the tube wall as the size of the sand particles. CNS) A4 specification (210X297 mm). 40- 536551 A7 B7 V. Description of the invention (38).  (Technical data compiled by the Japan Society of Mechanical Engineers. Fluid resistance of pipes and catheters. (Showa 5. 4), 32, Japanese Mechanical Society). Typical examples of smooth materials when ε is 1 mm or less are various metal materials such as stainless steel II and copper, and materials other than metals such as Si C, diamond:-, aluminum nitride, silicon nitride, and ceramic refractories. In addition, under manufacturing conditions such as flow rate and temperature, special conditions and high temperature and extremely high flow rate conditions, in order to maintain the same smoothness as the original material, a cooling structure can be added so that it can reach the present invention. Within the specified range to produce carbon black. For example, when using metal, if the temperature of the internal combustion gas is higher than the heat-resistant temperature of the metal, a structure such as a water cooling jacket can be used to cool it from the outside. In this way, when a material with a smooth surface is used as the material of the choke tube portion, it is possible to easily produce aggregates and carbon black in which the aggregates are distributed in a preferable range. In addition, the reason why a specific substance is used as the inner wall of the choke tube to obtain a carbon black having a uniform aggregate diameter without a large aggregate diameter can be roughly classified into the following factors. ^ Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) First, the micro-aggregation system is generated by the aggregation of micro-particles, so various conditions can be adopted to make the particle size distribution more concentrated. That is, the method of introducing hydrocarbon raw materials in a high-speed watershed is preferred. Secondly, in the process of agglomerating carbon blacks, in addition to the scramble action, the main reason is that the heavier aggregates are caused to collide with each other due to the movement caused by this scrambled flow. The present invention provides Each part of the manufacturing device during the carbon black aggregation process is provided with a disturbing flow suppression device, so the generation of large aggregates can be suppressed. This paper size applies Chinese National Standard (CNS) A4 (210X297 cm) -41-536551 A7 B7 V. Description of the invention (39) That is, the present invention can meet (Read the notes on the back before filling out this page). The mixing conditions are rapidly mixed with the high-temperature combustion gas, and the conditions of the reaction zone region after the carbonization of primary carbon particles and aggregates after gasification and temperature rise are uniform, and in order to prevent the introduction of hydrocarbon raw materials and After the reaction of the generated carbon ^ black primary particles colliding to form aggregates, during the period when the carbon black particles and the aggregate surface are sufficiently solidified without causing the fusion due to the collision, the cross-sectional shape of the flow path is greatly changed. The invention of conditions such as high disturbance caused by changes, even uneven surfaces on the inner surface of the choke tube and vortex disturbance caused by high-speed gas impact and peeling. The aggregation system of the Neem Carbon Black, which is an employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, is decomposed and condensed into droplets after the hydrocarbon raw materials are thermally decomposed, forming a nuclear precursor and generating primary particles, and then the particles collide with each other. And through collision with each other melted carbonized material. The present inventors found that when comparing the case of controlling the distribution of aggregates with the case of controlling the particle size distribution, it was found that the former requires a longer period of control. This series of particles are produced by aggregation in the liquid-phase hydrocarbon stage in the process, but the generation of aggregates is such that the liquid-phase particles are polymerized into a solid reaction temperature region under a collision and melting state to form a solid. It takes considerable time to solidify the hydrocarbons in this liquid phase at high temperatures. It is known from various test results that the time required to generate particles is generally 2 to 5 times. If the length of the choke tube part, or the length of the hydrocarbon material introduction position to the choke tube part outlet is more than the specified 値 above, and the choke tube has a specific material and a specific structure, the aggregate diameter, particle size and distribution can be all Keep in a specific range. At this point, the interior of the choke tube is composed of smooth surfaces, and the use of the device for a long period of time does not damage the internal smoothness or prevent the inner diameter of the choke tube. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm): 42- 536551 A7 B7____ V. Description of the invention). That is, when carbon black is manufactured using the manufacturing equipment having the above-mentioned choke structure, the production reaction of carbon black can be obtained by combining the above-mentioned requirements. That is, the use of the choke tube having the specific structure of the present invention can prevent degradation of the choke tube portion at a high flow rate, and can stably produce carbon black having relatively low-temperature characteristics. In addition, Japanese Patent Application Laid-Open No. 3-3 3 1 6 7 discloses that carbon black with a relatively concentrated particle size distribution can be obtained by maintaining the choke tube at a certain length. However, the effect on the aggregate distribution of the most important factors affecting the characteristics of carbon black has not been recorded, and only the preferred size of the diameter of the choke tube is 7 to 10 inches in diameter. The characteristics are different. In the present invention, if the length of the choke tube is set to a specific value or more, a carbon black having a small aggregate diameter and a very concentrated distribution without generating a large aggregate diameter can be obtained, which is completely the same as the invention described in the aforementioned publication. different. The temperature at which the hydrocarbon is introduced is preferably 180 ° C or higher, more preferably 1900 ° C or higher, and most preferably 2000 to 2400 ° C. In this way, a carbon black having a small particle diameter, a small aggregate diameter, and an extremely concentrated distribution can be easily produced. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs {Please read the precautions on the back before filling out this page) The carbon black aggregation system is thermally decomposed from hydrocarbon raw materials, condensed and condensed into droplets, and forms a nuclear precursor. A primary particle is generated, and then the particles collide with each other, and the carbonized material is melted by the collision. This reaction is carried out at a high temperature and a speed higher than a certain speed, so that the resulting particle size can be made smaller. In addition, since the carbonization rate is extremely fast, the time during which primary particles collide and solidify to produce aggregates is shortened, and the aggregates can be made smaller. Therefore, the temperature of the introduction site of the hydrocarbon raw material is in order to enable the hydrocarbon raw material to comply with the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 43-536551 A7 B7___ at the paper scale. Thermal decomposition and in the case of extremely high temperatures where small particle size carbon black is desired, the temperature of the present invention is best within the above-mentioned temperature range _20 is the temperature of the introduction site of the hydrocarbon raw material Within the above range, for example, in the region of the first reaction zone, oxygen can be added to the air when a high-temperature combustion gas stream is formed. Of course, the method of increasing the temperature of the combustion gas is not limited to the addition of oxygen, and may be performed by, for example, preheating the air. Among them, the temperature in the furnace can be performed, for example, by setting a radiation thermometer. In order to uniformly disperse the hydrocarbon raw material in the furnace, it is preferable to introduce the hydrocarbon raw material by providing two or more nozzles. In this way, carbon black having a particularly small aggregate diameter can be obtained. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) According to the carbon black manufacturing method of the present invention described above, the aggregate diameter carbon black aggregation system can be made from hydrocarbons After the raw materials are thermally decomposed, they are condensed and condensed into droplets, which form a nuclear precursor and generate primary particles, and then the particles collide with each other and melt and carbonize the material through the collision with each other. Indexes of aggregates that have been well known in the past include c D B P or centrifugal precipitation method of water dispersion of carbon black, electron microscope analysis method, etc. Recently, the size and distribution of aggregates are often measured by centrifugal precipitation method. In the embodiment of the present invention, as an indicator of whether the aggregate diameters are concentrated, the maximum frequency of the Stox-equivalent particle size distribution of the aggregates obtained from the centrifugal sedimentation method is the Stox-equivalent particle size Dm0d and the maximum frequency. The half width of Stox equivalent particle size, the ratio of D 1/2, D 7 5 is an evaluation without large aggregate diameter. The manufacturing method of the present invention described above can be efficiently produced: zp This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ΓZΓ ----- 536551 A7 B7_ V. Description of the invention (12 ) The half-width of the maximum frequency Stox-equivalent particle size and the maximum frequency Stox-equivalent particle size of the aggregate Stox-equivalent particle size distribution of the aggregate obtained by centrifugal precipitation method with an average particle size of less than 25 nm. The ratio 値 'of Di / 2 is the ratio D of Di / 2 / Dmd is 0.  6 or less ..., the ratio of the volume 75% diameter to the "mod" D 7 5 / Dm0d is 1 · 3 or less, small particle size, small aggregate diameter and extremely concentrated aggregate diameter distribution, and has a small size Carbon black of aggregate diameter material. In addition, carbon black having an average particle diameter of 20 nm or less which can increase the P v C blackness can be easily produced. In addition, according to the manufacturing method of the present invention, a particle diameter of 5 to 25 nm, more preferably 8 to 17 nm, N2SA is 100 to 700 m2 / g, more preferably 120 to 700 m2 / g, and cDBP is 40 to 110cc / 100g, more preferably 50 to 80cc / g,

Dm〇d is 10 to 70 nm, more preferably 20 to 50 nm, D1 / 2 is 10 to 50 nm, more preferably 10 to 30 nm, PVC blackness is 3 to 35, more preferably 5 to 35 Carbon black with a dispersion index of 1 to 200, more preferably 10 to 150. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) According to the method of the present invention described above, the average particle size can be made below 13 nm and DmOd is Furnace black with a ratio of Di / 2〆Dm0d below 0 nm and below 0.6. Furnace black refers to carbon black produced by the furnace method. The obtained furnace black is a substance which can exhibit extremely high blackness in particle size, aggregate diameter and distribution. In addition, the furnace black produced by the furnace method has the above characteristics, so it can avoid the problems caused by the pipe method, and is very suitable for industrial use.

In addition, because it has an average particle size of less than 14nm, the paper size of N2SA / SEM applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 45-536551 A7 B7 V. Description of the invention) The specific surface area ratio is greater than 1 · 3, CDBP is 50CC / 100 g carbon black, so the blackness and dispersibility can be improved at the same time, and its safety is also very good, and because it is a furnace black, it can avoid the problems caused by the pipeline method. When preparing a coating composition, a resin group composition, and a rubber composition containing the carbon black of the present invention, characteristics suitable for the application can be exhibited. As described above, the carbon black of the present invention has excellent dispersibility in a diluent and has a very high degree of blackness. Various compositions prepared therefrom can have excellent characteristics. Moreover, the carbon black of the present invention is When ρ Η 値 is set within a specific range, a rubber composition having excellent abrasion resistance and a resin composition which is not easily deteriorated can be obtained, or the water-based coating composition can have an effect of preventing aggregation. As mentioned above, the carbon black of the present invention containing a composition containing excellent carbon black can be obtained by adding various diluents, which is a novel substance which has not existed so far, and this novel carbon black can be produced by the aforementioned manufacturing method Made simply. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) To obtain the coating composition of the present invention, the resin composition of the present invention, the rubber composition of the present invention, and the Except that the ink composition must contain the carbon black of the present invention, the required composition can be prepared by a known method. When a resin composition containing the carbon black of the present invention is to be prepared, the applicable resin is not particularly limited, such as various thermoplastic resins or thermosetting tree fingers, a mixture of these resins, or various additives such as fillers. Thing. Substances that are generally used for the preparation of resin compositions can be appropriately selected depending on the application. These resins can be added with the compounds of the present invention, and if necessary, they can be mixed. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 46- 536551 A7 _B7__ V. Description of the invention (44). * Practice. At this time, the rubber kneading machine is a commonly used machine, such as a batch type open type roller kneading machine, a batch type closed type Chinese kneading machine, a continuous spiral single shaft kneading extruder, and a two-axis kneading machine. Extruder, flail rotary single-axis mixing extruder, two-axis mixing extruder-extruder, etc. The content of carbon black can be determined by a known technique, and generally it is preferably 1 to 60% by weight. When a coating composition containing the carbon black of the present invention is to be prepared, the coating which can be used as a paint is not particularly limited, and for example, it can be applied to various oil-based coatings, alcohol coatings, synthetic resin coatings, and water-based coatings. And is not limited to a specific purpose coating, such as paint, oily enamel, phenol resin or maleic resin, alkyd resin coating, urea resin coating, alcohol coating, nitro paint, vinyl resin coating, acrylic resin coating, polyester resin Coatings, epoxy resin coatings, polyurethane resin coatings, tetrasulfide resin coatings, emulsion resin coatings, water-based resin coatings, etc. are applicable. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The carbon black of the present invention is as described above, especially when it is used to prepare water-based coating compositions. Therefore, when used in the preparation of emulsion paints, water-soluble resin paints or water-based resin paints, it can exhibit particularly remarkable characteristics. The carbon black content can be measured by a known technique, and is generally preferably 0.1 to 10% by weight. When a rubber composition containing the carbon black of the present invention is to be prepared, the carbon black of the present invention may be added to more than one natural rubber or synthetic rubber. At this time, it is generally better to add 30 to 150 parts of carbon black to 100 parts of rubber. According to this method, it is also possible to form a rubber with a small loss coefficient or a small amount of heat. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -47-536551 A7 · B7 V. Description of the invention (45) The rubber components used are not particularly limited, such as styrene butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, nitrobutadiene rubber, iso-butyl rubber, etc. Isoprene rubber, ethylene propylene rubber, polysiloxane rubber, fluorine rubber, chlorosulfonated polyethylene, chlorinated polyethylene, polysulfide rubber, urethane rubber, acrylic rubber, epoxy vinyl chloride rubber, acrylic Oxide rubber, ethylene-ethyl acetate copolymer, liquid rubber, polyalkylene sulfide, nitroso rubber, etc., and others such as natural rubber or various mixtures thereof can be used. Various additives may be added if necessary. The above-mentioned rubber component is kneaded after adding the carbon black of the present invention to form a rubber composition. The kneading machine can be a general rubber kneading machine, such as a roller kneading machine, a Chinese-style kneading machine, a continuous spiral or continuous rotating single-shaft kneading extruder, and a two-axis kneading extruder. Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives (锖 Please read the precautions on the back before filling out this page) When preparing the ink composition of the present invention, there is no special limitation other than the use of the carbon black of the present invention. ^ For example, various paints and solvents well-known in the past can be added and dispersed sufficiently. The carbon black of the present invention is particularly suitable for an aqueous ink composition and has excellent effects. For example, a method of dispersing various water-soluble paints such as alkali-soluble resins such as lacquer-based resins and hydrosol-type resins in water-soluble coal can be performed by a known method. The dispersion method is not particularly limited, and it can be carried out by using various known methods or adding various additives. However, as described above, to produce carbon black with small particles, it is preferable to perform the carbon black formation reaction at a high temperature. However, in order to obtain this particle, there must be a paper that can be used in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). Γ48 536551 A7 B7__ 5. The invention is approved to be resistant to the carbon black generation reaction. Oxidative environment and manufacturing furnaces that pass the high flow rate of combustion air flow. In the following, a problem that can solve this problem is to increase the introduction area of the raw material oil when the hydrocarbon raw material is introduced into a high-temperature gas stream to produce black, and it has excellent mechanical strength at high temperatures. A carbon black manufacturing furnace composed of furnace materials will be described, and a manufacturing furnace capable of efficiently manufacturing a small particle size and high concentration will be described. After the inventors failed to achieve the above-mentioned object and conducted an in-depth review, it was found that if a specific material is used in a part of the carbon black manufacturing furnace, the above problems can be solved, and the present invention has been completed. That is, in the present invention, in the process of producing carbon black by introducing a hydrocarbon raw material into a high-temperature gas stream, a furnace composed of at least a part of a furnace wall made of magnesium oxide and chromium refractory is used to produce carbon black. A manufacturing method and a manufacturing furnace in which at least a part of a part in contact with a high-temperature air flow is made of a magnesium oxide and chromium-based refractory. The furnace of the present invention is a furnace composed of at least a part of a furnace wall made of a magnesium oxide and chromium refractory. It is preferable that a part or all of the furnace wall which is in contact with the high-temperature air flow is formed of a magnesium oxide and chromium-based refractory. The preferred implementation status of the magnesium oxide and chromium-based refractory in this part of the furnace wall is, for example, printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the magnesium oxide and chromium-based bricks (please read the precautions on the back before filling this page) ) The blocks are spread over the inner wall. Of course, it can also be applied to this part by mortar. Among them, magnesium oxide and chromium refractory is an improved refractory of chrome refractory and magnesia refractory, which has excellent resistance in addition to higher temperature. The corrosion resistance of slag or molten steel is a well-known refractory for steelmaking furnaces, and its service temperature can reach 1650 ° C. In addition, when manufacturing carbon black, it must be resistant to severe conditions in contact with high temperature and ultra-high-speed gas. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -49- " " 536551 A7 B7 5. Description of the invention W) Persistence. In addition, the various parameters of the furnace shape are to control the various characteristics of the carbon black produced. Therefore, the furnace for manufacturing the carbon black must be processed into a complex and precise shape. The inventors learned that the magnesium oxide was obtained after thorough research. · Chromium refractory is a kind of excellent mechanical strength under ultra-high temperature under the environment of carbon black manufacturing, so it can meet the furnace used in manufacturing carbon black by ultra-high temperature reaction. Material requirements, and is an excellent furnace material. Magnesium oxide and chromium-based refractories are made of magnesium oxide and chrome iron ore. Generally, materials with more than 50% of magnesium oxide are called magnesia-chrome bricks, and materials with less than 50% are called chrome-magnesia bricks. When it is more, its heat resistance is higher, but its peel resistance is poor. The melting temperature of chrome-magnesia brick is about 230 ° C, and its safe temperature is below 100 ~ 2 0 ° C of the melting temperature, and it can also be used in a temperature condition exceeding 200 ° C, so it is preferred Chrome-magnesia bricks with melting temperature above 2 300 ° C and improved heat resistance and spalling resistance. Therefore, the composition of MgO · Cr series refractory is 30 ~ 95% by weight of MgO and 3 ~ 40% by weight of Cr203, preferably printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the back first) (Please note this item and then fill out this page)

Mg〇 55 ~ 80% by weight, Cr203 5 ~ 30% by weight. Others can also contain, for example? 62〇3, 厶 12〇3'〇80 and so on. In addition, the combined state of the composition can be divided into spiral, semi-spiral, linear and the like, and can be changed according to the use conditions and operating conditions. Hydrocarbon raw materials can also be introduced to reduce the temperature of the gas by thermal decomposition reaction. The furnace wall after the reduction environment of the introduction site is laid with a high-oxidation inscription. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -50 · 536551 A7 B7 V. Description of the Invention 鲊) Substances shall be treated accordingly. The above objectives can be solved by the following description. That is, at least a part of the manufacturing furnace wall is a carbon black furnace made of a magnesium oxide refractory. In the furnace wall, it is preferable that the whole or a part of the stern wall which is in contact with the high-temperature air flow is made of a magnesium oxide refractory. The form of the magnesium oxide refractory in the part of the furnace wall in the furnace wall is, for example, a method of laying the magnesium oxide brick on the furnace wall. Of course, the manner in which an amorphous magnesia brick is used as the inner wall of the part is also the scope of the present invention. In addition, because the magnesia-based refractory is used to obtain a large thermal expansion coefficient, the spalling resistance is often inferior to that of a general refractory. However, the inventors set the magnesia refractory on the inner wall of the furnace to 30. When it is ~ 5 Omm, cracks caused by spalling can be reduced, and a magnesium oxide refractory suitable for a carbon black manufacturing furnace was found. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Also, when the manufacturing furnace is running, the temperature rises: when the temperature decreases and the temperature during operation changes, the heating rate and / or the cooling rate is Above 80 ° C / h is preferred. The present inventors have found that the deterioration of the mechanical strength of magnesium oxide can be prevented, especially when the temperature rise and fall speed (heating speed or cooling speed) is lower than 80 ° C / h in the entire region from low temperature to high temperature. In addition, when the manufacturing furnace is in operation, it is preferable that the temperature rise rate and / or temperature decrease rate of the furnace temperature in the region of 800 to 130 ° C is 30 ° C / h or less. Especially at 800 ° C ~ 1 300 ° C where the brittleness / plasticity transition point of magnesium oxide can degrade the mechanical properties, it can prevent the deterioration of mechanical strength when the temperature rise rate is below 30 ° C / h. Significantly extend the life of the furnace. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -51-536551 A7 B7 _ V. Description of the invention 09) · As mentioned above, in a furnace-type manufacturing furnace, the reaction temperature can be increased to make carbon In the case where the quality and productivity of black are improved, the refractory temperature or the resistance to spalling of the manufacturing furnace has certain limits, so it is necessary to set a limit with a reaction bar_ί ¥. That is, when the oxygen-aluminum-based (high-alumina-based or ultra-high-alumina-based) refractory is laid as the internal refractory in the highest temperature part, if it contacts the refractory temperature (approximately 18 0 0 t) or more In the case of high temperature flow, the refractory material will fall off due to melting or cracking in a short period of time, and the problem that the operation cannot be performed occurs. In addition, other ultra-high temperature refractories, such as magnesium oxide, are well-known refractories. Among them, magnesium oxide has a high melting point of 2800 ° C and can withstand extremely high temperatures, but its thermal expansion rate is very large and its resistance to spalling is relatively In the past, the refractory was poor, so it has not reached the stage of practical application for industrial furnaces with extremely complicated designs. Therefore, when used as a carbon black furnace, the necessary characteristics such as chipping resistance and heat resistance are insufficient, resulting in extremely severe damage, making it difficult to put it into practical use. Printed by Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Contrary to this issue of ultra-high temperature refractories, it has been proposed to use various additives to add magnesium oxide or chromium oxide, etc. The method of improving the resistance to peeling of the substrate, and the inventors have reviewed the results and found that in addition to the reduction of the flame resistance of the substrate itself, the additives have reduced the resistance to cracking due to the scattering of the additives during long-term operation It is extremely difficult to maintain the characteristics of the carbon black manufacturing furnace itself. Others, for example, consider the use of bricks made of ultra-high-temperature refractory materials such as high-purity magnesia or zirconia, and build a furnace with a small proportion in consideration of the smallest amount of thermal stress, but this method will Squeezing makes the bricks fall off and shortens the life of the furnace. The burden on the working surface or the economic surface when the furnace is built or repaired is increased, and it is difficult to put it into practical use. This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -52- 536551 A7 B7___ V. Description of the invention feo). The invention described above is an invention to solve the above problems, that is, the invention is Provided is a high-quality, high-quality furnace material capable of maintaining high-temperature or shape-maintaining properties at a high temperature when carbon black is introduced into a high-temperature gas stream to generate carbon black. Makeup brow black making furnace. In order to achieve the above-mentioned object, the inventors have conducted intensive research and found that the use of at least a portion of the carbon black through a mold processing refractory material can solve the above problems and achieve the invention content described below. That is, as described below, when a hydrocarbon raw material is introduced into a high-temperature gas stream to produce carbon black, at least a part of the furnace wall is a manufacturing furnace composed of a mold material, and a carbon black generating reaction is performed by the manufacturing furnace. It is a manufacturing method of carbon black. Among them, the mold material referred to here refers to the dry powder obtained by mixing the monomers or particles of high melting point refractory materials such as magnesium oxide, chromium oxide, and alumina, and the mold processing is a pneumatic mold for the mold material. Or by vibration casting. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The following will explain the content of the present invention. The manufacturing furnace is a furnace composed of at least part of the furnace wall made of mold material. . The furnace wall is preferably the whole part of the furnace wall that is in contact with the high-temperature gas flow, or part of the furnace wall is a refractory processed by a mold. The form of the refractory processed by the mold in the furnace wall is, for example, a product obtained by molding the refractory having a high melting point such as magnesium oxide, chromium oxide, and alumina in the furnace wall. The mold material is preferably composed of at least one of magnesium oxide, chromium oxide, and aluminum oxide. Among them, the mold material obtained from magnesium oxide with a higher melting point is the most resistant to high temperatures, and is suitable as a material for high temperature manufacturing furnaces for carbon black. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -53-536551 A7 B7 5. Description of the invention (51). In addition, other than the mold materials listed in the above list, other materials such as chromium-magnesium refractory and magnesium-chromium refractory can be used as mold materials. …… I. When manufacturing carbon black, there is an urgent need for durability under the severe conditions of contact with high temperature and ultra-high-speed gas. In addition, the various parameters of the furnace shape are important indicators for controlling the various characteristics of carbon black, so complex and precise shape processing can be performed on carbon black manufacturing furnaces. The present inventors have conducted in-depth review. Using this mold material for mold processing can make carbon black at ultra-high temperature manufacturing conditions, because it has both excellent shape retention and heat resistance. It can meet the characteristics of the furnace material for manufacturing small-size carbon black and the characteristics of construction under ultra-high temperature reaction, so it is an excellent furnace material and construction method. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) as the refractory of the mold material. The higher the purity, the higher the heat resistance, but the worse the resistance to spalling. However, in the manufacturing furnace of the present invention, even if the spalling is caused by cracking of the mold material, the fracture surface is not a rough surface, so there is no shedding phenomenon. Therefore, it is better to perform the mold processing with the higher purity mold material while satisfying the required characteristics. In addition, generally speaking, the mold material is often sintered only when the surface of the furnace inner wall is heated at the temperature of the furnace, but the back surface is used without being sintered. This mold processing is known to be used in induction furnaces for dissolving metals. This may be because even if the surface of the sintered mold material layer is cracked due to thermal expansion, it can still be prevented by the unsintered powder mold material on the back side to prevent the melt Right. However, if the use temperature exceeds about 1 800 ° C, the crack width of the mold material becomes larger and deeper, so that this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 54- 536551 A7 __B7 V. Description of the invention) (Please read the note on the back side first and then fill out this page) The gap between the unsintered mold material on the back side will be enlarged, so that the molten stream will be out of the furnace. Therefore, the use temperature is limited to 1 8 ο good. On the other hand, a carbon black manufacturing furnace does not produce a melt, so it can be used in the sintered state on the backside. .. If the back surface of the mold material is sintered, in addition to cracking in the thickness direction, it will crack to the surface of the construction layer at a certain depth. Therefore, if the thickness of the construction material is 3 5 to 5 Omm, the mold material is not easy. Dropping occurs, so it has high shape retention. In addition, if the thickness is less than 35 mm, the mosaic area generated by the broken mold material is small and it is more likely to fall off. In addition, if the scoreline of the mold material described above is planned to a certain depth (for example, about 5 to 1 mm), the position of the crack can be set so that the refractory material formed by the mold will not form small fragments, so it has High shape retention. Or plan the inner wall surface of the furnace to a depth of 2 ~ 5 m / m and 3 0 ~ 4 0 0 mm &gt; &lt; A square groove of 3 0 0 to 4 0 mm is more advantageous. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. When the entire furnace is cast with refractory materials such as magnesium oxide and high heat-transporting chlorine, the thickness of the layers has increased significantly, making the furnace itself extremely large and uneconomical. Therefore, if only a low-heat-conducting refractory material such as a heat-shielding sheet or a heat-resistant brick is used for mold processing and the outer side is used as a furnace lining, the furnace itself can be miniaturized. If the inner wall of the furnace is laid with magnesia as a mold, and the secondary layer is constructed with refractory materials such as high alumina bricks, the magnesia will react with alumina to generate a low melting point compound, which will make the magnesia mold material refractory. Decreased, so the temporary decomposition temperature is below 15 0 ° C, or when the secondary layer of magnesium oxide mold material is magnesia-chrome brick, the critical temperature of the magnesia-chrome brick layer and the high alumina layer applies the Chinese national standard at this paper scale (CNS) A4 specification (210X297 male) -55-536551 A7 B7 _ V. Description of the invention) It is better to be below 150 ° C. In addition, the construction position of the mold material may be various parts of the entire furnace. In the second reaction zone region, the hydrocarbon raw material introduction region and the third reaction zone region, when the thermal decomposition reaction of the hydrocarbon raw material is performed, the gas temperature is reduced to form Under the factors such as reducing environment, it is better to lay conventional refractory materials such as high alumina bricks on the inner wall of this part. However, as mentioned above, since the flow velocity of the combustion gas in the introduction portion of the hydrocarbon feedstock is expected to increase, it is currently desired to achieve a manufacturing furnace in this state. The invention described below is to solve the problem that the pressure of the manufacturing furnace and the damage of the device can also make the flow rate of the combustion gas of the raw material hydrocarbon introduction part reach 0.  A goal of 8 ~ 1 Mach. In order to increase the flow velocity of the combustion gas at the introduction position of the liquid hydrocarbon raw material, the inventors have conducted various in-depth review results and found that the nozzle can be improved when the hydrocarbon raw material is introduced. * Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The nozzle for the introduction of hydrocarbon raw materials is located in the second reaction zone to introduce the hydrocarbon gas of carbon black raw materials. Set in the combustion gas for the purpose. Generally, it is cylindrical and has a pointed nozzle suitable for discharging hydrocarbon raw materials at the tip. When inserting into the furnace, it is preferable to use a sleeve with a cooling structure that is resistant to high-temperature combustion gases. Generally, the flow velocity of the gas in the furnace in the direction of the furnace axis can be measured by dividing the actual flow rate of the combustion gas by the cross-sectional area of the furnace at the measurement position. The inventors have obtained through research that if the diameter of the hydrocarbon raw material introduction nozzle is larger than the furnace cross-sectional area of the nozzle insertion position, the cross-sectional area of the hydrocarbon raw material nozzle insertion position can be greatly reduced due to the hydrocarbon raw material nozzle itself. The dimensions are applicable to China National Standard (CNS) A4 specifications (210X297 mm). 56-536551 A7 B7 V. Description of the invention), and then accelerate the flow velocity of the combustion gas passing through the front of the nozzle to 〇.  Mach 8 to 1. That is, the present invention described below uses a high-temperature combustion gas stream and a first reaction / band region formed by the mixed combustion of an oxygen-containing gas 1Ϊ fuel and then mixes the obtained high-temperature combustion gas stream with a hydrocarbon raw material. In the method for producing carbon black in a method for producing carbon black, a second reaction zone region having a gas choke tube section and a third reaction zone region located downstream of the second reaction zone region to stop the reaction is produced in the second reaction zone. One or more nozzles for introducing hydrocarbon raw materials are provided in the belt region. The effect of reducing the cross-sectional flow area through the setting of the nozzle protruding into the furnace can reduce the cross-sectional flow area of the hydrocarbon raw material introduction part, and further Manufacturing method and apparatus for accelerating the flow velocity of combustion gas passing through the front of the nozzle to 0.8 to 1 Mach carbon black. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The invention described below is a specific section of the furnace section where the hydrocarbon is introduced into the nozzle. That is, when one or more nozzles for introducing hydrocarbon raw materials can achieve the effect of reducing the flow area of the cross section, the cross section of the combustion gas in the introduction section of the hydrocarbon raw materials can be made because the nozzles are protruded in the furnace. Reduced flow area. This point will be described with reference to FIG. 9. FIG. 9 is a cross-sectional view of A—A. The circled part is that the flow area of the cross-section (that is, the area of the oblique line A of the part where the combustion gas passes in the section of the furnace) is substantially reduced due to the protrusion of the hydrocarbon raw material introduction nozzle shown in B. , And then increase the flow velocity of the combustion gas passing through the front end of the hydrocarbon feedstock nozzle. The cross-sectional area is reduced by the protruding ratio of the hydrocarbon material introduction nozzle, and the paper size is applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 57 · 536551 A7 B7____ V. Detailed description of the invention Increasing the speed to the desired level 'i.e.' accelerates the flow velocity of the combustion gas passing through the front of the nozzle to Mach 0.8 to 1 which is thought to protrude the nozzle to reduce the cross-sectional flow area by more than 30%. In addition, the ratio of the protrusion of the nozzle is to reduce the cross-section and flow-movement area by 30 to ¾ or more, preferably 50% or more, and more preferably 60% or more. Through the simple operation of introducing the hydrocarbon raw material into the front end of the nozzle and protruding out of the furnace, it is possible to reduce the pressure loss of the combustion gas stream in an ultra-high-speed manner without using the complicated peripheral equipment often used in the past. Industrial significance. In addition, since the raw material introduction nozzle has an additional part such as a cooling jacket, if it protrudes inside the furnace together, it can also reduce the furnace section to a certain degree. The reduction rate of the cross-sectional flow area is the ratio of the cross-sectional area of the raw material hydrocarbon introduction nozzle portion to the cross-sectional area of the furnace containing the hydrocarbon raw material introduction portion. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). For example, the diameter of the furnace where the hydrocarbon raw material introduction nozzle is 60 mm, and the number of the hydrocarbon raw material introduction nozzle is 2. The outer diameter of the nozzle is 60 mm, and the front end of the nozzle is inserted into the furnace 20 mm, that is, the cross section of the gas passing portion is as shown in FIG. 9. When there is no nozzle, the cross-sectional area of the furnace at this part is about 2827 mm2. Because the nozzle with an outer diameter of 60 mm is inserted, about 159 mm2 of the furnace is covered. This section is actually the cross-sectional area that the combustion gas can pass through. Is 1 1 7 7 mm2, that is, the section area of this part is about 4 1.  6%. The flow rate of the combustion gas in the furnace is divided by the actual flow rate of the combustion gas. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -58-536551 A7 B7 V. Invention description fee).  Obtained by the cross-sectional flow area. The speed of sound in a pipe often varies depending on the temperature or the composition of the combustion gas. Assuming that the temperature of the combustion gas is 1800 ° C, the speed of sound is about 913m / s. And when the average cross-sectional flow velocity of the gas in the second region is 3 ·· Om / s, the impact of the above-mentioned hydrocarbon raw material introduction nozzle makes the flow velocity of this part of combustion gas increase by 2.4 times. It is about 840 m / s, which is about 0.92 Mach. As mentioned above, the flow velocity of the combustion gas in the second reaction zone region other than the hydrocarbon feed material introduction site is about Mach 38. The normal velocity, due to the role of the hydrocarbon feed introduction nozzle, the flow of the hydrocarbon feed spray introduction site The speed can exceed the current Mach 0 · 4 ~ 0 · 8, reaching an almost unimaginable speed of Mach 1. Therefore, after the hydrocarbon raw material is introduced into the furnace, the hydrocarbon gas flows at a high speed after being introduced into the furnace. The atomization of the combustion gas makes the hydrocarbon raw material finer, which can cause the evaporation of the hydrocarbon raw material and the reaction of carbon black formation. Faster, as a result, carbon black with extremely small particle size and aggregate diameter was obtained. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In this example, the number of nozzles for the introduction of hydrocarbon raw materials is two. For other cases, such as the diameter of the pipe or the diameter of the nozzles for the introduction of hydrocarbon raw materials, it can also be targeted The same effect can be achieved by adding or removing several nozzles in the furnace. In addition, the flow velocity of the combustion gas is accelerated to a position close to the speed of sound, only in a very short area near the periphery of the hydrocarbon raw material nozzle, so that the pressure loss can be suppressed to a minimum. This point can be compared with the case where the flow velocity of the combustion gas is increased to nearly Mach 1 due to the protrusion of the supply nozzle of the hydrocarbon raw material. -59- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7_ V. Inventive color 7) Reduce the diameter of the entire second reaction zone without protruding the nozzle and increase the flow rate of the combustion gas to Mach 1 The pressure loss caused by the whole furnace is compared for confirmation. However, because the comparison between the two requires a large amount of time and energy, computers are generally used to analyze and compare the flow of cooking. The flow analysis of the present invention is performed using a difference method and is analyzed using a commonly used commercial fluid analysis program. For example, the damage to the interior of the furnace caused by the kinetic energy of the combustion gas generated by this method is limited to the front end of the nozzle, so it can maintain low equipment maintenance costs even if it is operated for a long time. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The carbon black manufacturing device applicable to the present invention, as long as it has the above-mentioned features that can reduce the cross-sectional flow area caused by the introduction of hydrocarbon raw materials The device can be used, especially when the length of the pipeline is more than 50 mm. When a manufacturing furnace having such a length is used, if the flow rate of the combustion gas at the position where the hydrocarbon raw material is introduced is increased to 0.8 to 1.0, a carbon black having excellent black envy dispersion can be obtained. In addition, when using this manufacturing furnace having a long pipe portion, it is possible to solve the problems such as the loss of the extreme pressure caused by the conventionally known method in order to increase the speed at which the hydrocarbon feedstock is introduced. The third reaction zone region is sprayed with water using a nozzle 7 for introducing a reaction stop fluid in order to cool the high-temperature reaction gas to 100 to 800 ° C. The cooled carbon black can be carried out by a generally known method such as trapping a filter bag and separating and recovering the gas. As mentioned above, the inner wall surface of the pipe is preferably smooth, and the angle of the entrance of the pipe is preferably 45 ° ~ 100 °, but it is subject to high temperature due to the high temperature. This paper's dimensions apply to the Chinese National Standard (CNS) A4 Specifications (210X297) 嫠 536551 A7 _B7_ V. Detailed description of the invention) It is extremely difficult to maintain the desired shape for the parts hit by high-speed flowing combustion gas. For example, if the material of the pipeline is made of high-purity alumina or refractory containing alumina and chromium oxide or calcium oxide and lanthanide-element oxide as high-temperature stabilizer, and combustion gas above 180 ° C When contacted, the shrinkage of the part due to temperature or hot air flow will cause extremely significant damage or deformation, so it is extremely difficult to produce carbon black that can maintain an appropriate form. The above-mentioned materials that can withstand high temperatures above 18,000 ° C are generally the best refractory materials with chromium oxide or magnesium oxide and magnesium oxide and chromium oxide as the main components. However, even if this material has a temperature of 180 ° When the flow rate of the internal gas reaches above 10 Om / s, the reduction of the furnace wall caused by the glass peeling on the surface of the furnace cannot be avoided. Therefore, it is extremely difficult to maintain an appropriate reactor type. . Therefore, the material of the gas barrier is a material that must be resistant to high temperature and high-speed airflow damage when manufacturing carbon black with extremely concentrated aggregate distribution. However, the previously known refractory materials cannot meet this requirement, so it cannot be manufactured continuously. High-quality carbon black is also a current problem. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back before filling this page). Methods to prevent damage or deformation of the gas barrier, such as JP 4 4 1 3 1 9 2 or JP Sho 4 7-5 6 3 describes a method of using a metal structure having a cooling structure with cold coal on the outside as a gas barrier pipe. Indeed, using a metal structure with a forced cooling structure as the gas barrier can greatly suppress the thinning of the furnace wall and properly maintain the shape of the gas barrier tube portion, but when cooling the outside of the narrow portion formed by the metal structure, It was found that the size of the carbon black aggregates became much larger. This may be due to the low temperature. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) · 61.  536551 A7 B7_ Fifth, the description of the invention is fine) The heat generated on the metal surface becomes larger, and the temperature in the area where carbon black is generated is significantly reduced. Therefore, the time for liquid carbon black to solidify and carbonize is longer, and carbon black is increased. The number of agglutination times between each other will produce carbon black which is aggregated to be more developed. -Currently known methods to control the size of carbon black aggregates, such as adding alkali metal compounds such as potassium to the hydrocarbon feedstock to suppress its structure, but if it is used as a resistor formed by the above-mentioned metal structure with a forced cooling structure In the process, a large amount of alkali metal compounds must be added. This will cause a significant increase in impurities such as alkali metal salts contained in carbon black. This should also be the optical adaptability or dispersion state and electrical characteristics of carbon black additives. Cause of deterioration. Specifically, if the amount of the alkali metal compound added is increased from 2000 to 1,000%, the result will cause the impurity content of the inorganic compound in carbon black to increase by 2 to 10 times. A carbon black with a very high impurity content often causes problems such as poor dispersibility, which is not conducive to various suitability, especially the effect of carbon black with low DBP oil absorption is more significant, so it is known that the production of DBP oil absorption is 80 c 6 / Carbon black with low oil absorption below 1 Og is extremely unsuitable. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) In addition, under the high-speed airflow generated by the combustion gas above 180 ° C, a section of carbon must be maintained In the manufacturing equipment for the high-speed flow time of black formation, it is necessary to keep the condition of abrasion and deformation low for a long period of time, so that the temperature unevenness of the generation system in the carbon black generation region is suppressed, and the overall temperature must be avoided. Reduced characteristics. The inventors have thoroughly studied the above problems and learned that a carbon black manufacturing device with a specific choke tube structure can solve the above problems, and further, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -62 · ~ 536551 A7 B7 V. Description of the invention feo) (Please read the notes on the back before filling this page). That is, as described below, the present invention uses a choke tube portion formed by including a front section portion of a hydrocarbon material introduction position and a subsequent rear section portion thereof, and the front section portion has a strong cooling structure, and the rear section and the The difference in the inner diameter of the front part is a carbon black structure device with a choke structure within 5-0% of the front part, and the method for producing carbon black by it. When using a manufacturing device in which the end of the first reaction zone area and the continuation of the second reaction zone area are tapered or rapidly reduced, or the two share the same shape to form a choke tube in the second zone area, it can be burned. The gas is accelerated, so that in addition to being able to accelerate to a higher flow rate of 2 5 Om / s (preferably 300 m / s or more) suitable as carbon black, it can also react with hydrocarbons in the second reaction zone. The ingredients are thoroughly mixed. At this time, in order to make the hydrocarbon feedstock react at a high speed at the feedstock introduction position, the taper before the feedstock introduction can be reduced by more than 10 ° or it can be made into a very shrinkable state to improve its miscibility. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs has printed the choke tube section of the present invention. The device with the inner diameter difference from the front section is within 50% of the front section. In addition, the size of the inner diameter of the posterior section of the choke tube and the anterior section may be larger or equal. In this way, a device with a forced cooling structure in the front section can be made more important. The material of the front part is preferably metal. Because it is easy to cool, it can prevent the inner wall from being damaged or deformed during cooling, and can maintain the smoothness of the inner wall, so it can uniformly generate carbon black in the choke tube section, and can continuously make paper. The paper scale is applicable to Chinese national standards (CNS ) A4 size (210X297mm). 03- 536551 A7 _B7__ V. Description of Invention 铷).  Carbon black with extremely concentrated size distribution was obtained. The cooling method of the front part is not limited, as long as it can prevent the inner wall of the choke tube from being damaged or deformed and maintain its smoothness. Generally, if the device is located outside the narrow area and has a forced cooling structure, or if it has a hip casing structure, such as a metal casing structure with high thermal conductivity, cold coal such as liquid or gas is circulated in the anterior casing area for forced cooling. The resulting device. A device having a forced cooling structure such as a sleeve and a portion in contact with the narrow portion is a sleeve formed of a metal or an inorganic compound having a high heat resistance temperature. The length of the front section is from the position where the hydrocarbon material is introduced to the front section of the narrow section, that is, the distance between the front section of the choke tube and the rear section, preferably 30 to 300 mm, and more preferably 50 to 200 mm. In addition, the difference between the inner diameters of the front part and the inner part is less than 50% of the inner diameter of the front part, and preferably 30% or less. The latter part is preferably formed in the form of a refractory material. More preferably, the length of the rear part of the refractory material 7 with a softening point of 18,000 ° C or more is 500 mm or more, and more preferably 700 mm or more. Due to the rapid gasification of hydrocarbons mixed with high-speed airflow and high-temperature combustion gas in the printed choke tube portion of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, the hydrocarbons obtained by gasification are completely mixed with the combustion gas within a dwell distance of tens of mm In addition to reaching a sufficient temperature for the start of the reaction, the temperature of the mixed gas can be rapidly reduced. The actual measurement of the temperature of each reaction site and the analysis of the reaction to each temperature equilibrium state show that most of the heat of the combustion gas is consumed by the heating and gasification of the hydrocarbon raw materials. In each of the above conditions, the introduction of hydrocarbon raw materials is high. -64 · (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7__ V. Description of the invention ㊃2).  After the rapid gas flow, the gas is mixed and gasified, and the distance between the mixed gas and the cooling is 50 to 100 mm from the position where the hydrocarbon feedstock is introduced. The gasification is almost completely completed. &gt; It is also known that the mixing speed of the airflow 1 at a flow rate of 2 50 m- /… s or more is completed at an early stage and is mixed with the surrounding high-temperature combustion gas to reduce the overall mixing temperature of the mixed gas by 2 0 0 Above ° C. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The invention has a cooling structure in the front section of the choke tube, so it can prevent deformation, damage or maintain high smoothness of the choke section. On the other hand, due to the cooling structure, there are problems with the past, such as the increase in the amount of carbon black agglomeration caused by the heating of hydrocarbon raw materials and the decrease in temperature after gasification, or the resistance to carbonization introduced The hydrogen raw material can be heated in the first reaction zone and vaporized at a temperature where it is mixed with the introduced high-temperature combustion gas, and the durability can be improved in the portion including the refractory having a cooling structure. The rear part of the choke tube is generally a region of reaction gas below 16 0 ° C, so you can use, for example, alumina-based refractory with less silicon content, or alumina-chromium oxide-based melting point of 190. Refractory materials above ° C can solve the above problems while suppressing heat generation. Therefore, in the present invention, the distance from the introduction position of the hydrocarbon raw material to the contiguous part of the front section and the rear section of the choke tube section is set to 0 ~ 300 mm, which is considered that the combustion gas temperature of the hydrocarbon raw material is mixed and gasified. The reduction has been reached, so this method can suppress the increase in the size of the aggregate. This pair of high-temperature gas above 1 800 ° C has heat resistance and can be resisted, and the device is resistant to abrasion caused by the turbulent flow of high-speed airflow, that is, the surface obtained by adding the wear resistance of general metal is cooled by It can reduce the heat-resistant temperature to the standard of this paper (CNS) A4 specification (210X297mm) · g5 _ 536551 A7 B7 V. Description of the invention) Device made of metal structure below 8 0 ° C, The preferable setting part is about 50 ~ 100 mm from the screen surface of the gas blocking part to the introduction of the hydrocarbon raw material. In the following areas, because of the cold phenomenon caused by the hydrocarbon raw materials, a heat-resistant material of 1 800 ° C can be used ... and the fluorine temperature in this area has not been significantly reduced, so the surface temperature can withstand 80 The manufacturing equipment of different materials (characteristics) composed of refractory materials such as high alumina at a temperature of about 0 ~ 1 0 0 ° C is preferred, and this area is preferably set at the rear part of the choke tube. In addition, the material of the front part of the choke tube is preferably a material whose surface can be cooled to reduce the temperature and improve the heat resistance. The structure of forced cooling is not necessarily limited to the metal with a high thermal conductivity. It can also be coated with highly heat-resistant inorganic compounds such as alumina and silicon. It is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. When the above methods are used to maintain the temperature in the furnace at a temperature above 2000 ° C, judge Correct furnace temperature is extremely important. Because the temperature in the furnace has a direct relationship with the quality of carbon black, if the temperature in the furnace is too high to exceed the heat-resistant temperature of the furnace wall, it will cause damage to the furnace wall and make the operation impossible. · Therefore, the current high temperature in the general furnace is set to about 180 ° C, and the thermoelectric pair is usually directly inserted into the furnace to measure the temperature of the gas. However, if the temperature inside the furnace exceeds 180 ° C, the thermocouple cannot be directly inserted into the furnace to measure the temperature. For measurement methods exceeding 18 0 ° C, for example, radiation thermometers and light thermometers can be used, but the temperature cannot be measured correctly. -66- (Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standards (CNS) A4 (210X29 * 7mm) 536551 A7 B7 __-___ V. Description of the invention It is to provide a method for efficiently producing carbon black with excellent color strength and rubber reinforcement at a high temperature above 180 ° C in the furnace. Although the temperature of the inner surface of the furnace wall is higher than Furnace wall material is above the refractory temperature, but to prevent and prevent the damage of the furnace wall material-the temperature of the gas in the furnace that was impossible to measure in the past. The invention described below is to provide a method for efficiently producing carbon black with excellent coloring strength and rubber reinforcement at a high temperature of 180 ° C or higher in the furnace. The temperature is higher than the refractory temperature of the furnace wall material, but the temperature of the gas in the furnace is to prevent the material of the furnace wall from being damaged by the refractory temperature. The present inventors have conducted an in-depth review of the above-mentioned problems, and have found that the temperature in the furnace can be accurately measured by a specific method even if the temperature in the furnace is above 180 ° C. That is, the invention described below involves measuring the temperature of the gas inside the furnace and / or estimating the temperature of the furnace wall using a thermoelectric pair embedded in the inner wall of the furnace wall when manufacturing carbon black using a carbon black manufacturing furnace using a furnace method. The step is a method for producing a characteristic carbon black. ^ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The inventors have gone through a variety of correct furnace temperatures to estimate the correct furnace temperature above 180 ° C As a result, it was found that the method of burying the thermoelectric pair in the furnace wall and judging the temperature in the furnace based on the measured temperature was the most correct method. The present invention is applicable to any manufacturing furnace used for producing carbon black. Specifically, in a carbon black manufacturing furnace using a furnace method, it is more suitable to measure the temperature in the furnace or the temperature of the furnace wall. Generally, the furnace can release heat to the outside due to natural or forced external cooling. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 7〇γZ ~ &quot; 536551 A7 B7 V. Description of the invention (65) A temperature curve is generated inside the furnace material constituting the furnace. Even when the temperature near the inner wall of the furnace reaches a high temperature of 180 ° C, the temperature inside the furnace wall is lower than this temperature, so the thermoelectric pair is buried in the interior of the furnace wall. Immediately afterwards, the temperature was measured at the site. -A ^ The measurable temperature is generally divided into 2 forms. One is the wall surface temperature of the inner wall of the refractory furnace, and the other is the temperature of the combustion gas in the furnace. The temperature of the inner wall of the refractory is extremely important for the damage of the refractory, and the temperature of the combustion gas in the furnace is a decisive factor for the quality of the carbon black produced. The present inventors have found that the temperature of the above two types can be estimated from the thermoelectric pair embedded in the furnace wall. First, the temperature of the furnace inner wall can be estimated by the heat transfer calculation method. The thermal conductivity of the material of the furnace wall is known because of the known temperature, and its temperature is changed by the temperature. The basic formula for the calculation of heat conduction is Q = AA △ D / L. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) This is called the Fourier calculation. Where Q is the amount of heat conduction per unit time, λ is the thermal conductivity, A is the area through which heat passes, ΔΤ is the temperature difference between 2 points, and L is the distance between 2 points. Basically, the calculation of heat conduction is based on this formula. In fact, the shape of the furnace is also very complicated, so the heat conduction method is also a third power method, and the heat conduction method is different due to the shape of the furnace. And the thermal conductivity of the material of the furnace wall is known as described above and varies with temperature. Therefore, the internal temperature of the furnace wall is measured by using the finite element method as a computer simulation method, and the method of estimating the temperature of the internal wall surface of the furnace is the paper standard. Applicable to China National Standard (CNS) 8-4 specification (210X297mm) "68 · 536551 A7 B7 V. Description of invention) The more correct method. At this time, the furnace shape should be correctly molded and the temperature of the thermal conductivity should be considered Dependency is better. The finite element method used here is generally used in scientific calculations.… Secondly, the estimation of the temperature of the gas in the furnace-,-This method can also be carried out by computer simulation. General furnaces can be The natural or mandatory external cooling method releases heat to the outside through the furnace wall, causing a temperature difference between the temperature in the furnace wall and the temperature of the gas in the furnace. The inventor used a computer to analyze the thermal fluid to calculate the temperature of the furnace wall and the gas in the furnace. The temperature difference. Therefore, the method of estimating the temperature of the gas in the furnace based on the temperature of the furnace wall is determined. In this calculation formula, the conduction of the gas in the furnace to the heat and convection and the furnace The radiant heat generated by burning flames and gases is taken into consideration. The difference method used in the calculation method is also used in general scientific calculations. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before reading) (Fill in this page) In the method of measuring the temperature of the combustion gas in the furnace by the temperature of the furnace wall, the above method is generally better to install two or more thermoelectric pairs in the furnace wall. Also, at this time If it is set according to the normal direction of the axis of the furnace, the heat release between 2 points can be measured: At this time, one end of the thermoelectric pair is closer to the inner wall of the furnace. The other end is set to The low temperature side of the same refractory. In this way, the temperature can be controlled under the temperature of the furnace inner wall and the temperature of the gas in the furnace. Generally, to obtain high temperature combustion gas at a temperature above 2000 ° C, at least One of the air or hydrocarbon raw materials is heated first, or a combustion-supporting gas such as a gas containing more oxygen is used. The former is used to control the air and the temperature of the combustion gas and the furnace wall. The degree of hydrogen fuel preheat the way of this paper scale applicable Chinese National Standard (CNS) A4 size (210X297 public H. 09- 536551 A7 B7_ V. Description of Invention 7) · Go on. That is, if the temperature of the combustion gas and the furnace inner wall is too high and the temperature is to be lowered, the degree of preheating is reduced. If the temperature is to be increased, the degree of preheating may be increased. In addition, the latter uses more oxygen-containing gas. It is performed by controlling the oxygen content and the fuel supply amount. That is, if the temperature of the combustion gas and the furnace wall is too high and the temperature is to be reduced, the oxygen concentration is reduced. And fuel supply, if you want to increase the temperature, increase the oxygen concentration and fuel supply. Give. In this way, in a way that the combustion temperature in the furnace does not damage the material of the furnace wall and can maintain the highest temperature, carbon black with excellent coloring power and rubber reinforcement can be efficiently produced without damaging the material of the furnace wall. As described above, in order to obtain carbon black with a small particle size, firstly, a hydrocarbon raw material must be sprayed into a high-speed airflow in a gas blocking pipe part of a reaction part, and the liquid raw material is atomized by using the motion of the gas and thermal energy. And by using the turbulent flow in the reaction section to mix them, the thermal energy of the high-temperature combustion gas can be used to efficiently perform the carbon black generation reaction. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The combustion chambers in carbon black manufacturing furnaces can be of various types, and their materials can generally be high-temperature stainless steel and other high-temperature metals. Generally speaking, as long as it can reach 1700 ° C, it can be used in the oxidizing environment of carbon black manufacturing. However, a temperature exceeding 1700 ° C is a very dangerous situation for the combustion chamber used in current carbon black manufacturing equipment, which is likely to cause damage to the combustion chamber caused by melting damage and thermal distortion. temperature. For example, Japanese Patent Publication No. 4 4-3 9 9 6 describes a carbon black manufacturing furnace having a fuel hole and a combustion-supporting gas hole in a refractory and a diffusion combustion device in a combustion chamber. Exceeding the size of the refractory material This paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm) ~ 7〇1 ~~ &quot; &quot; 536551 A7 £ 7_ V. Description of the invention (68).  It is extremely difficult to use when the temperature of the material is higher than the heat-resistant temperature. Can withstand heat-resistant materials above 2000 ° C (such as chrome-oxygen-based refractory materials, magnesium-chromium-based refractory materials, magnesium oxide-based refractory materials, etc.) in high-oxidation environments of carbon black manufacturing furnaces. The problems of rapid temperature change, or the damage of the refractory material caused by the corrosion of the high-speed air flow when the fuel holes and the combustion-supporting gas holes are refractory materials, make the aforementioned materials difficult to put into practical use. The present invention described below is for the purpose of providing a combustion chamber and a manufacturing apparatus having resistance in a method for producing carbon black from a high-temperature gas. The inventors have repeatedly and thoroughly studied the above problems, and as a result, they have learned that when a combustion chamber having a dance structure is used to generate combustion gas, a smaller primary particle size, smaller aggregate diameter, and aggregation can be obtained. Carbon black with excellent characteristics with a small volume distribution range and few large aggregation systems is prepared according to the following description. That is, the invention described below is a combustion chamber for producing carbon black having a cooling jacket structure, a method for producing carbon black using the same, and a manufacturing apparatus including a combustion section, a reaction section, and a reaction stop section. , A carbon black manufacturing device for a combustion chamber having a cooling jacket structure and the like. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The invention described below uses a combustion chamber in a manufacturing device consisting of a combustion section, a reaction section, and a reaction stop section. A device for manufacturing carbon black with a specific structure. The manufacturing device consisting of the combustion section, the reaction section, and the reaction stop section itself is a well-known device, and therefore it can be appropriately selected by known techniques. For example, it is comprised by the manufacturing apparatus shown in FIG. The invention described below is characterized by a cooling jacket structure in the combustion chamber. Fig. 4 is a schematic view of an example of a combustion chamber having a cooling structure. Figure I Paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -71 &quot; 536551 A7 B7_ V. Invention description 9) (Please read the precautions on the back before filling this page), 21 is cooling Sleeve, 22 is the cooling medium inlet nozzle, 23 is the cooling medium outlet nozzle, 24 is the atomizing part, 24-1 is the convex part, 24-2 is the combustion gas spray hole, and 24-3 is the combustion gas inlet hole 25 is a flange, 26 is a 0 ring, 2 7 ·· is a set screw, 2 8 ^ is a reed for fixing the atomizer, 29 is a fuel introduction hole, 210 is a fuel introduction flange, and 2 1 1 is a combustion assisting The gas is introduced into the nozzle. The cooling sleeve is a cylindrical double-layer structure provided outside the combustion gas introduction pipe of the combustion sleeve, and the double-layer structure is internally connected with a combustion atomizing section and the combustion atomizing section also has a cooling structure. The material of the double tube and the atomizing portion is preferably a material having good thermal conductivity. The material with good thermal conductivity herein refers to a material having a thermal conductivity of 1000 kcal / m h r ° C or more, and specifically, copper, copper alloy, aluminum, and the like. The cooling jacket faces the furnace, and other materials can be used for the part with high temperature. The cooling jacket has a double-layered structure and has a structure that cools the combustion chamber with a cooling medium flowing in the direction of the arrow as shown in the figure. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. If the double tube and atomization department is equipped with a temperature detection timer that can detect the temperature at the equivalent temperature, the cooling state of the front end of the combustion chamber can be accurately grasped and the operation can be performed stably. And under the control of temperature, the amount of cooling medium can be adjusted to the most suitable for the operation. That is, it is a method of maintaining the operating system at a high temperature with a minimum amount of cooling medium before raising the heat generation to a minimum to obtain a high temperature. Generally, it is difficult to use one combustion chamber for operation in the low temperature region to the high temperature region. Therefore, more than two combustion chambers are used to increase the temperature to the high temperature region. In this state, the atomizer can be applied to the paper size of the Chinese National Standard (CNS) A4 (210x297 mm) in various temperature regions. -Ϊ́ΐ 536551 A7 B7 V. Description of the invention and dedicated atomization At this time, when the inner surface of the outer tube of the cooling jacket is in contact with the outside of the atomizer, the heat exchange can be performed more efficiently, and the front part of the cooling tube is cooled when it contacts the high temperature environment. When the contact surface is parallel to the i-axis direction, it is difficult to remove the atomizer. This is the structure formed by the inner diameter of the outer sleeve of the cold muscle sleeve and the outer diameter of the atomizer part after adjustment, and the two parts are brought into contact through thermal expansion. If the contact surface is convex, under high temperature conditions It is also easy to exchange the combustion chamber. When the projection angle is 60 degrees or less, there is no problem. Among them, 1 degree to 10 degrees is preferable. In order to maintain good contact between the atomizer and the protrusion at the front end of the cooling jacket, the atomizer is fixed with a fixed spring. This fixing force is irrespective of the way it is constituted as long as it can have a reed-like driving force as shown in FIG. Also, as long as the gasket structure of the flange portion is a gasket having the same properties as the 0-ring, it can be used. For example, a sealed tank structure using a gasket is a structure that can maintain the sealability. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The new and useful carbon blacks and their manufacturing methods with both blackness and dispersibility are as described above. However, after examination by the present inventors, it was found that the carbon black currently present has the following problems. That is, when the carbon black produced by the current method has an average particle diameter in a region below 14 nm, or a small particle diameter with an average particle diameter of about 8 to 13 nm, the inverse ratio between the particle diameter and the blackness The relationship disappears. Therefore, even if the particle size is reduced, the blackness of the resin or coating has no effect, that is, the blackness of a certain degree or more cannot be obtained. For example, the inventors found that, as a transparent soft PVC-73- (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 536551 A7 B7_ __ V. Description of the invention (Π) Visual comparison of colorant and carbon black when mixed directly 'If it is also compressed DBP oil absorption is 7 Om 1/1 0 0 g in carbon black, the particle size is l When comparing between 〇nm and 12nm, I3nm, and 15nm, except for the blackness between 15 nm and 13 nm, which has a large visual experience-other, such as between 13 nm and 12 nm and 10 nm are completely There is no difference. It is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). At present, in addition to the particle size or aggregate diameter that can affect the blackness, some people have suggested that Method for attaching functional groups on the surface of carbon black particles. For example, it is described in Japanese Patent Publication No. 4 6-1 8 3 6.8 that carbon black is oxidized with ozone to increase the blackness of the ink system. However, the functional groups attached to the surface of carbon black obtained by the method of imparting functional groups will adsorb functional groups or polar atomic parts held by lower molecular weight paints such as inks or coatings, and form a paint phase on the surface of carbon black. Change the refractive index of light. This is a method to improve the optical suitability to prevent carbon black from agglomerating during curing. However, if the solvent has alkyd resin, melamine resin, phenol resin, etc. The polymerizable low-molecular-weight resin has an effect on only a part of the ink or coating paint, but it is almost dispersed when dissolved in a thermoplastic resin composed of a high molecular polymer, or it is dispersed in For lacquers or mineral oil-based lacquers, such as acrylic resins or styrene resins, which have few functional groups and weak polarities, even if they are subjected to a known surface treatment such as oxidation and given functional groups, they will not have blackness. Make an impact. The inventors have analyzed various phenomena related to blackness in particles with a smaller particle size of less than 14 nm, and made various research results to improve the blackness. It is known that in carbon black with small particle diameter, the original Optical original blackness of small particle size carbon paper size applies to Chinese National Standard (CNS) A4 specification (210X297 cm) = 74- 536551 A7 B7 V. Description of the invention (72) The reason why black cannot be used in the dispersion system One reason is that as the particle size of carbon black decreases and the specific surface area increases, the cohesiveness of the surface of carbon black increases significantly, so that the carbon black cannot be fully separated. This result can infer the reason why the carbon black degree cannot be fully exerted. In order to improve the method, the method may be as follows: 1-In order to reduce the cohesiveness of the surface of the carbon black, the surface is modified so that it does not easily aggregate even with a high specific surface area. After various reviews, it was found that this cohesiveness is closely related to the amount of oxygen-containing volatile components per unit surface area. For example, if the nitrogen adsorption surface area lm2 given to carbon black is 0.  3 When the amount of oxygen-containing volatile components above 5mg, the carbon black with a large specific surface area undergoes oxidation treatment and has little effect on the blackness in the soft PVC system under the significant reduction of the carbon black cohesiveness. Carbon black with weak cohesiveness has higher blackness than carbon black without surface modification. 2 . The surface modification of the above 1 is not based on the total amount of volatile components but the volatile content per unit area as an influencing factor. If one is used, it is generated in carbon black before the oxidation. When the carbon black is activated at a high temperature for a long time to make it porous and has a larger specific surface group than other carbon blacks of the same particle size, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the back first) Note: Please fill in this page again.) To meet the conditions of 1, you must give more volatile components, and then you must add a lot of oxidizing materials or you must increase the oxidation time, so it will reduce its economy. In addition, when using oxidants such as nitric acid and nitrogen dioxide to oxidize, when the oxidation temperature is high or the oxidation time is long, if the volatile constituents are to be reacted with the oxidation reaction, when the oxidant is activated to increase the specific surface area, Without increasing the volatile content per unit area, carbon black with weak cohesion cannot be obtained. In this way, in addition to 1, the surface size of the oxidized surface is modified to the Chinese National Standard (CNS) A4 specification (210X297 mm) -75: 536551 A7 B7_ V. Description of the invention (73) For smaller and less cohesive carbon black, the roughness factor (N2SA / S EM ratio) of the carbon black must be reduced to less than 2 · 5 before the oxidation treatment, and the roughness factor (N 2 SA SEM ratio) after the oxidation treatment is Below 2 · 8, preferably -2 ·. · 5 or less. -The ratio of the specific surface area of N2SA / S EM. The specific surface area of N2SA and SEM can be obtained separately, and then the ratio 値 can be calculated. N2SA is determined in accordance with ASTM d3037-88. The SEM specific surface area is calculated by the following formula. SEM = 6000 / (p · dA) p: Specific gravity of carbon black (1 · 86g / cm3) dA: Volume-area particle size (nm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) (Fill in this page again.) 3 · Summarize the above 1, and 2 to review the relationship between the characteristics of carbon black and the degree of blackness obtained from various oxidation treatments. It is known that the unit area on the surface of carbon black is deficient in addition to the amount of volatile components and roughening The amount of iodine attached also affects the blackness. That is, when the ratio 碘 of iodine adhesion amount / nitrogen adhesion specific surface area (N 2 SA) is small, the blackness of the resin addition system is higher, and the ratio of iodine adhesion amount / nitrogen adhesion specific surface area (N2SA) is ··. When it is below 5 it will become near saturation. From the above three points, a method of obtaining high blackness can be obtained. When one or more methods are combined, the blackness of carbon black with a small particle size can be significantly increased, so that a composition having a very high level of blackness can be obtained. That is, the following carbon blacks have a blackness that is unachievable so far. The paper size is applicable to the Chinese National Standard (CNS) 84 (21 × 297 mm). 76- 536551 A7 WJ_ V. Description of the invention W) · Degree. (1), with 0 per unit area. 35mg / m2 or more volatile • Carbon black with two or two components and a particle size of 14 nm or less. (2) Roughness factor (N2SA-/ -S E Μ ratio) is 2 &lt; Carbon black described in (1) above 8 below. (3) Carbon black described in (1) or (2) above when the ratio of the iodine adhesion amount / nitrogen adhesion specific surface area (N2SA) is 0 · 4 5 or less. (4) When cDBP 値 is 50cc / 100g or more, the carbon black described in any one of items 1 to 3. When producing carbon black with higher volatility, use the two stages of surface treatment and oxidation treatment of the carbon black produced to make the volatile components adhere to when the carbon black base material is not sufficiently oxidized. The manufacturing steps are preferred. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs {Please read the precautions on the back before filling out this page} In the manufacturing steps of the carbon black base in the previous paragraph, particles with an average particle size of 14 nm or less must be used. Especially carbon black particles of 8 ~ 1 3 nm. When the particle size exceeds 1 4 nm, the cohesiveness of carbon black is significantly reduced, and the correlation between the decrease in cohesiveness and the blackness can hardly be judged from the surface properties. It has been known in the past that only polymerizable paint can be improved by surface modification. The affinity with carbon black makes the series that have an effect on optical suitability due to the adsorption of the paint effective. This is related to the wide improvement of optical suitability due to the decrease in the cohesiveness of carbon black. (1) to (4) The content is different. In particular, when the particle diameter is 13 nm or less, the cohesiveness of carbon black fails to make full use of the blackness in almost all dispersion series. Therefore, it is learned that the current paper size, which is different from the improvement of current technology and the affinity of lacquer, is to reduce the carbon black cohesiveness directly by oxidation treatment. The national paper standard (CNS &gt; A4 specification (210X297)) is 77 · 536551 A7 B7_ 5. Description of the invention k) The method also has excellent effects. Here, the average particle diameter refers to the average particle diameter of each particle diameter obtained by an electron microscope method. Others, for example, the compressed DBP oil absorption (c D Β) of carbon black also has a great impact on the cohesion of carbon black. When the nD BP is low, the cohesion of carbon can be greatly increased, even if surface properties are modified to improve the cohesion. Sex, it has not been able to obtain sufficient results. Therefore, in order to exhibit high blackness, the cDBP of carbon black should be at least 500 m 1/1 000 g or more. The carbon blacks of (1) to (4) above use N2SA / SEM specific surface area of 2 · 8 or less, more preferably 2 · 5 or less, and the coarse noise factor (N2SA / The carbon black produced by controlling the S EM ratio) to 2.5 or less is preferred. The carbon black of the above (1) to (4) is not particularly limited in its aggregate diameter, and it is preferable that Dm0d is 80 nm or less, and more preferably 50 nm or less. The aggregates gradually show effects under the above-mentioned range of dispersibility and blackness. The carbon black of the present invention is adjusted to a specific particle size, a specific N2 SA / S EM specific surface area ratio, a specific pH 値, and a specific c DBP, Then, it can exhibit the characteristic that D mod is 80 nm or less, preferably 50 nm or less. The print of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is even better. The ratio of the half frequency of the maximum frequency Stox equivalent particle size D 1/2 to the maximum frequency of the Stox equivalent particle size Dmod 値 D i / 2 When / D ^ is adjusted to 0 · 6 or less, preferably 0 · 5 or less, excellent and excellent blackness can be obtained, and the degree of dispersion can be increased. In the range of carbon black in (1) to (4) above, the volume is 7 5% of the radius. The ratio of the radius D 7 5 to Dmod is 値. If D 7 5 / Dmod is adjusted to 1.6 or less, it is preferably 1.3 or less. At this time, this carbon black may have an adverse effect on dispersion. -78- {Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) Central Standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 536551 A7 B7_ V. Description of the invention W) The content of large aggregates with a volume exceeding 7 5¾ is reduced to a very low range. In addition, the present inventors, when producing a composition containing various carbon blacks, have invented a fluidity at high shear rate with high blackness, excellent dispersibility, and excellent fluidity, and can prevent aggregation-of- Carbon black. This carbon black is the carbon black described below. (5) The average particle diameter is 25 nm or less, the standard error / average particle diameter ratio of the particle size is 0. 35 or less, Dm0d is 80 nm or less, D i / 2 / Dmad is 0.6 or less, and N2SA / Carbon black characterized by a ratio of SEM specific surface area of 2.8 or less. (6) The carbon black according to (5), characterized in that pH 値 is 5 or less. (7) The carbon black according to (5) or (6), characterized in that the average particle diameter is 15 nm or less. (8) The carbon black according to any one of (5) to (7), characterized in that the ratio of the iodine adhesion amount (IA) / nitrogen adhesion specific surface area (N2SA) is less than 0.5 mg / m 2 —, And IA (mg / g) <Volatile (mg / g) + 0.1XN2SA. (9) The carbon black according to any one of (5) to (8), characterized in that cDBP is 50 m 1/1 00 g. The carbon black in the above (5) to (9) has an average particle diameter of 25 nm or less, preferably 8 to 15 nm or less. When the particle size exceeds 25 nm, the blackness of carbon black decreases significantly, and it is almost impossible to reach the so-called "blackness" of chromaticity. Among them, in order to achieve significant blackness, it is best to be 15 nm or less. This paper size is applicable to the national standard (CNS) a4 specification (210X297 mm) -79- (Please read the precautions on the back before filling this page) '536551 A7 B7 V. Description of the invention W) Carbon black with small particle size If there are a large number of carbon blacks with an average particle size of more than 15 0¾ in the particle size distribution, the large black carbon black will cause the blackness to decrease significantly. In order to avoid this phenomenon, “the large particle size carbon black which is the cause of the reduction in i degree must be reduced to very low”, that is, the ratio of the standard error D σ of the particle size distribution to the average particle diameter 値 D σ / D It should be at least 0. 4 5 or less, and preferably 0. 4 or less. Carbon black with extremely concentrated particle size and high blackness can be obtained. The term "average particle diameter" as used herein means the average particle diameter of the primary particle diameter determined by an electron microscope method. If the carbon black in the above (5) to (9) must have a high blackness, the aggregate diameter Dmod of the carbon black is 80 nm or less, preferably 50 nm or less. This is because if the aggregate diameter exceeds 80 nm, it is extremely difficult to produce carbon black with extremely high blackness. In addition, the distribution of aggregate diameter is closely related to the degree of blackness and dispersion. Therefore, in order to achieve a balance between the degree of blackness and the degree of dispersion, its maximum frequency is half of the size of the equivalent particle size of Stoxx, which is 1/2 and the maximum frequency. The ratio of the tox equivalent particle size 〇 ^ factory / 2 / 〇_ If adjusted to 0.6 or less, preferably 0.55 or less, the blackness and dispersion can be balanced. 0 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling out this page). Among the carbon blacks (5) to (9) above, the volume is 75% of the radius D75 to Dmod ratio 値, D75 / Dmod 値 is preferably 1 · 6 or less, more preferably 1.3 or less. This substance can reduce the content of large aggregates with a volume of more than 75% which has an adverse effect on dispersibility to an extremely low range. The carbon black described above has an N2SA / SEM specific surface area of 2.8 or less, and more preferably 2.5 or less. The temperature at the time of carbon black generation is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) · 80 · 536551 A7 B7 in the pipe method and paper size as the particle size becomes smaller in the furnace method The temperature tends to increase. In the pipe method with poor thermal mixing, the temperature is higher than the surrounding gas, so even if it is carbon black with the same particle diameter, the carbon black produced by the pipe method is more active. This may be the reason why it is a carbon black with a high specific surface area. The average temperature for the formation of carbon black below 25 nm is at least 12 0 ° C. At this temperature, carbon black will rapidly promote the activation reaction. At this time, it has a great relationship with the roughness. In particular, when carbon black with a particle size of less than 15 nm is generated, the temperature of the surrounding gas can reach above 15 0 ° C, and a rapid activation reaction can be generated in the residence time of about 5 to 20 ms after the formation of carbon black. Significantly increased specific surface area. The carbon black surface can make the surface porous during the activation reaction. Therefore, it can absorb more resin or lacquer components and solvents than the original smooth surface. In this way, free resin or The reduction of lacquer and solvent makes the viscosity of the dispersion system significantly increase. This porosity has a great relationship with the ratio of specific surface area N2S A / S EM of carbon black called rough factor. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) N 2 SA / SE Specific surface area ^ ratio, you can first obtain the specific surface area of N2SA and SEM separately, Then calculate its ratio. N2SA is determined in accordance with ASTM d3037-88. The SEM specific surface area is calculated by the following formula. SEM = 6000 / (p · d A) P: Specific gravity of carbon black (1 · 8 6 g / cm 3) dA: Volume-area particle size (nm) This paper size applies Chinese National Standard (CNS) A4 specification (210X297嫠) ΤβΤΖ 536551 A7 B7 V. Description of the invention) · When the N2SA / SEM specific surface area exceeds 2 · 8 or more, for example, in a dispersion system containing more than 20% by weight of carbon black, only a slight change in the amount of addition can be used. The viscosity of the dispersion system changes greatly, so it is extremely difficult to make a composition with a stable viscosity. In addition, the resin main ingredients obtained by adding this carbon black at 40% by weight or more will greatly increase the torque of kneading due to the increase in viscosity during dispersion, making it more difficult to knead. This high viscosity main ingredient is In practice, it is not easy to dissolve in other resins during the dilution step, which makes the optical characteristics or strength characteristics significantly deteriorate, which is not conducive to practical use. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). In order to suppress this roughness, it is extremely important to set the retention time after the carbon black is generated until the reaction stops. Among them, the content of aromatic hydrocarbons that have a great adverse effect on safety during the period until the reaction stops can greatly affect the progress of the carbonization reaction of carbon black. If the reaction stop period is shortened, the hydrocarbon raw material can be changed from The time until supply of carbon black and the generation of agglomerated carbon black containing a large amount of aromatic hydrocarbons cause a dehydration reaction due to temperature generation, which shortens the carbonization time, resulting in carbon black that contains too many aromatic hydrocarbons. Safety is degraded, so the reaction stop of carbon black is to stop the carbonization reaction near the complete stop, and to cool it to a temperature below 1 200 ° C without activating the reaction. Roughness can be both. In addition to the conditions for stopping the reaction, the inventors have made in-depth studies on the reasons for the development of the roughness of carbon black, and know that the ratio of the specific surface area of N2 SA / S EM of carbon black is much larger than the particle size of carbon black. The distribution has a stronger effect. Carbon black generation and carbonization time, that is, the start time of the activation reaction after carbonization. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -82 · 536551 A7 B7 _ V. Description of the invention Bismuth). Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the precautions on the back before filling this page). There are great changes depending on the particle size of the carbon black. In the case of carbon black with a larger particle size, the time it takes to start the generation is later, and because the ambient temperature is very close to the carbon black particles that are formed, the carbonization time is more required. Therefore, the carbon black produced has a very wide particle size distribution and contains-a large number of carbon blacks with an average particle diameter of 150% or more. Therefore, in order to complete carbonization of carbon blacks with an average particle size of more than 150%, the time to stop the reaction must be postponed, and the reaction will generate and produce carbonization below the average particle size faster than this reaction. Carbon black starts the energization reaction early, and more disadvantageously, these small particle size carbon blacks are surrounded by extremely high temperatures, so the energization reaction proceeds earlier. This result will make carbon black with a very wide particle size distribution and less aromatic hydrocarbons observed under an electron microscope. It can be clearly seen that carbon black with a smaller average particle size is in a state of porosity, especially granules. The carbon black particles with extremely small diameters have all appeared in a "nest" state. On the other hand, carbon black with a long carbonization time and a large average particle size hardly exists, and carbon black with a small average particle size that was activated earlier hardly exists. Therefore, the carbon black with extremely concentrated particle size distribution, that is, the ratio of the standard error D σ ′ of the particle size distribution to the average particle size D, Dcr / D is suppressed to 0.45 or less, preferably 0.4 or less, to suppress the above (5 ) ~ (9) The roughness of the carbon black. In order to produce such carbon black with extremely concentrated particle size distribution, it is necessary to generate carbon black under a highly miscible environment under conditions of extremely uniform temperature distribution and hydrocarbon raw material distribution. In addition, the compressed DBP oil absorption (cDBP) of carbon black has a great impact on the cohesion of carbon black. When c DBP is too low, the cohesion of carbon black is greatly improved, even if the surface properties of carbon black are modified by the effect of the present invention. The quality paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -83- 536551 A7 B7____ 5. Description of the invention 蚋) In order to improve cohesion, sufficient results cannot be obtained. Therefore, the cDBP suitable for the above (5) ~ (9) carbon black should be at least 50ml / (please read the precautions on the back before filling this page) above 100 g. 〇 Printing by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs It is known that some paints for coatings or inks are used to improve the dispersion properties, dispersion stability, and viscosity characteristics of carbon black. For example, Japanese Patent Publication No. 4 6-1 8 3 6 8 describes that the ink obtained by oxidizing carbon black with ozone can increase the blackness. These carbon blacks with extremely acidic functional groups on the surface can adsorb functional groups or polar atomic parts of lower molecular weight paints such as inks, and the formation of a paint phase on the surface of carbon black causes the refractive index of light to change or cure. It can have the effect of improving optical suitability due to the aggregation of carbon black. In particular, in inks or paints in which some highly polar copolymerizable low-molecular-weight resins such as alkyd resins, melamine resins, and phenol resins are dissolved in the solvent, if a small-particle-size carbon black with high cohesiveness is used on the surface, When a functional group is attached, it is not practical to use the carbon black because P Η 値 is 5 or less because the viscosity increases sharply or the blackness and gloss decrease due to the re-aggregation of carbon black during hardening. This effective dispersion system that can absorb the components of polar paints. When reviewing the surface properties and dispersion suitability of carbon black, we know that the viscosity or dispersion stability, various optical properties, etc. have a balance on the adsorption capacity and cohesiveness of carbon black paints. Considerable impact. In more detail, the amount of acidic functional groups representing the known volatile content has a great influence on the paint's adsorptivity, so the carbon black produced by the adsorption is often mixed with the paint, making the carbon black difficult to access, which hinders it. Coacervation. In addition, in the ratio of carbon black's iodine adsorption amount to specific surface area, which has an inhibitory effect on carbon black cohesiveness, carbon black is less likely to agglomerate when the iodine adsorption amount per surface area is low. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -84- 536551 A7 B7 V. Description of the invention) The tendency is too low. In addition, in terms of the ratio of the iodine adsorption amount to the specific surface area and the amount of acidic functional groups, the ratio of the iodine adhesion amount (IA) / nitrogen adhesion specific surface area (N 2 SA) is 0.5 mg / m 2 The following two and full S ------IA / N2SA <Volatile matter (mg) / N2SA + 〇 1 will not cause the phenomenon of agglutination of adsorptive paint system, and has good suitability. This method uses oxidizing agents to suppress the development of roughness during surface oxidation and oxidation to achieve surface oxidation treatment. The temperature is set at 50 ° C ~ printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) Please fill in this page again) At 200 ° C, contact the nitric acid gas with the carbon black in a short time between 10 seconds and 600 seconds in a reactor that can uniformly mix carbon black and nitric acid gas. After the carbon black is oxidized, the temperature is rapidly reduced, or it is separated from the gas containing nitric acid and nitrogen dioxide to achieve it. After this method, the oxidation treatment shows that the roughness and particle size distribution of the above (5) are suppressed. Carbon black with a small particle size and a small aggregate diameter with a relatively concentrated collective distribution has the characteristics of excellent dispersibility, dispersion stability, fluidity, and good blackness. The carbon black described in (5) to (9) above, in particle size, particle size distribution, aggregate diameter, aggregate distribution, N2SA / S EM specific surface area ratio, iodine adhesion amount (IA) / nitrogen adhesion specific surface area (N2SA When the ratio of), pH 値, and c DBP are set within a certain range, carbon black compositions having excellent balance of optical suitability, dispersibility, dispersion stability, and viscosity can be prepared from various dispersion systems. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) _85: 536551 A7 _, _B7_ V. Description of the invention) (Please read the precautions on the back before filling this page) Also, the inventors Analyze the factors that affect the dispersion action, blackness, and fluidity of the carbon black matrix with a small particle size of less than 16 nm with higher blackness, and obtain higher blackness and superior dispersion compared to previous work Various kinds of researches on carbon black with low viscosity and low viscosity ... i As a result, we know that the distance between the pores and mobility and the carbon black aggregates in the dispersion, that is, the number density and function of carbon black and the difference between carbon black Cohesion has a great relationship. In the former, if the density of the number of fine aggregates is increased, the fluidity will be adversely affected, and the aggregation force of the latter will increase the density of oxygen-containing functional groups on the surface of carbon black, or cause inorganic substances that cause iodine adsorption. The activity decreases and tends to weaken. That is, if the amount of volatile matter on the surface area of carbon black is high, carbon black with a low amount of iodine adsorption per unit surface area is less likely to aggregate and tends to reduce viscosity. In more detail, if the unit surface area lm2 of carbon black contains 0.35 mg or more of oxygen-containing volatile components, carbon black with a small particle size also has the ability to significantly reduce the viscosity of the dispersion system, and the balance between the two 値, iodine adhesion Amount (IA) / Nitrogen Adhesion Specific Surface Area (N2SA) is 0.5 mg / m2 or less, and printed by IA / N2SA, a consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs &lt; Volatile matter (mg) / N2SA + 〇 · 1 can disperse carbon black and extremely reduce viscosity. This can greatly improve the shortcomings of inevitability, the poor dispersibility and poor fluidity obtained by using carbon black with a small particle diameter with a balance of blackness and dispersibility and high D B P oil absorption. In terms of blackness and dispersion, 'because fine aggregates also have a bad influence on dispersion, and large aggregates have no influence on blackness. -86-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7___ 5. Description of the invention ") Good effects, etc., so it is better to use carbon black with fine aggregates without fine aggregates or large aggregates. This carbon black has high blackness and excellent dispersibility. That is, Carbon black with small particle size, small aggregate diameter, and extremely large aggregate diameter, among which carbon black without extra-large aggregate diameter, etc. have high blackness and #good dispersibility. That is, the above-mentioned blackness can be easily solved. The problem cannot be achieved with the degree of dispersion. This is a surface oxidation treatment method that is balanced and uses an oxidizing agent to suppress the development of roughness during the oxidation reaction. The temperature is set between 50 ° C and 2 0 t. In a reactor that can uniformly mix carbon black and nitric acid gas, contact the nitric acid gas and carbon black within a short time of 10 seconds to 600 seconds to make the carbon black oxidize, then quickly reduce the temperature, or Nitrate The separation of acid and nitrogen dioxide is achieved by this method. After oxidation treatment in this method, it is known that the roughened and particle size distribution of the above (5) is suppressed. The carbon black with a small aggregate size and a small aggregate diameter is more concentrated in the aggregate distribution. It has the characteristics of excellent dispersibility, dispersion stability, fluidity, and good blackness. In this way, it is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Carbon Black Economy (please read the precautions on the back before filling this page) (10) Carbon black with a particle size of 16 nm or less, a Di / 2 / Dmod ratio of 0.6 or less, and a volatile component per unit area of 0.35 mg / m2 or more. (11) Particle size of 16 nm or less The D1 / 2 / Dm0d ratio is 0.6 or less, the ratio of the iodine adhesion amount (IA) / nitrogen adhesion specific surface area (N2SA) is 0.5 mg / m2 or less, and IA (mg / g) &lt; Volatile matter (mg / g) + 〇 · 1XN2SA (m2 / g) o This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 cm) Second 536551 A7 B7 V. Description of the invention) ( 1 2) The carbon black according to any one of (10) to (1 1), whose cDBP is 50 c c / 100 g or more. (13) As described in any one of (10) to (12), the carbon black has a DmOd of 80 nm or more. -(1 4) The carbon black according to any one of (10) to (1 3), wherein the D 7 5 / Dmd ratio is 1.6 or less. (15) The carbon black according to any one of (1) to (14), wherein the D75 / Dmod ratio is 1.3 or less. In order to manufacture this highly volatile carbon black, the steps of manufacturing the mother carbon black without sufficient oxidation treatment, and the oxidation treatment of the produced carbon black in controlling surface properties to perform the process of imparting volatile components A two-stage manufacturing step such as an oxidation step is preferred. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The steps in the previous paragraph regarding the manufacture of the mother carbon black without sufficient oxidation treatment should first have an average particle size of 16 nm or less. The best is 8 ~ 1 3 nm. When the particle size exceeds 16 nm, the blackness will decrease, which is almost the same as the blackness of the commonly used color carbon black. In particular, when the particle diameter is 1 3 nm or less, almost all dispersion systems cannot fully exhibit the blackness due to the cohesiveness of carbon black. This is different from the improvement of the conventional technology and the affinity of lacquer, and is treated by oxidation. It is more effective to directly reduce the cohesiveness of carbon black. The term "average particle diameter" as used herein refers to the average particle diameter of the primary particle diameter determined by an electron microscope method. Carbon black's compressed DBP oil absorption (cDBP) has a great impact on the aggregation of carbon black. When c DBP is too low, the aggregation of carbon black will increase significantly, even if the aggregation is improved by modifying the surface properties. Can get full results. Therefore, in order to make the best carbon black with high blackness, the paper size applies the Chinese National Standard (CNS) A4 specification (210 &gt; &lt; 297 mm 1 -88-536551 A7 B7 V. Description of the invention (86). cDBP should be at least 50ml / 100g. (Please read the precautions on the back before filling out this page.) In the carbon blacks of (10) to (15) above, the aggregate diameter Dm〇d is 80 nm or less, preferably 50 nm or less. The effect of aggregate diameter on the dispersion and blackness can be gradually understood ... i. Carbon black with specific particle size, specific N2SA / S EM specific surface area ratio, specific c DB P, etc., with Dmu of 8 0 nm or less, more preferably a range of 50 nm or less. More preferably, the ratio of the half-width of the maximum frequency Stokes-equivalent particle size 0 1/2 to the maximum frequency of the Stokes-equivalent particle size Dmod, D i / 2 / Dmd is 0 or less, and more preferably 0. · Below 5 5 can get excellent blackness and higher dispersion. In addition, the ratio of the volume 75% radius 075 to 0 is 値 75/0 ,. &lt; 1 値 is preferably 1 · 6 or less, and more preferably 1 · 3 or less. This substance can reduce the content of large aggregate diameters exceeding 75% by volume which has an adverse effect on dispersibility to an extremely low range. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs The above-mentioned novel carbon blacks (ί) ~ (1 5) can be used as various carbon black compositions. Typical examples include paints, inks, resins, and rubber compositions. The manufacturing method can be appropriately adopted as described above. The method of manufacturing (1) to (1 5) above these small particle diameter carbon blacks can be, for example, furnace black or pipe black produced by known manufacturing equipment, but if the method of producing pipe black is at a high temperature containing oxygen, When manufacturing in a combustion gas, it is extremely difficult to suppress roughness, so it is preferable to use a substance prepared by a furnace method as a base material. The furnace method can efficiently produce small black carbon black with high blackness ^ Paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -89- 536551 A7 _____ B7_ V. Method of Invention (87) For example, the method described above can be used. Therefore, when using the small particle size carbon black prepared by the above method as the base material, in order to make the volatile content per unit surface area be 0.35 mg / m2, the oxidation treatment shown below can be used. -Said carbon black. Oxidation treatment of volatile components that can increase the specific surface area. If there are too many volatile components, the specific surface area generated at the same time will be suppressed. The ratio of the specific surface area of N2SA / SEM after the oxidation treatment is less than 2 · 8, which is better. It is 2 · 5 or less. While suppressing the increase of the specific surface area, it is better to suppress the iodine active point of the carbon black surface with stronger cohesiveness. In order to make the volatile components, specific surface area, and iodine absorption into a balanced state, the time when the oxidant and carbon black coexist at a temperature exceeding 100 ° C is shortened, and the reaction to impart volatile components is carried out when necessary. Under both conditions, an oxidation method using nitric acid gas as an oxidizing agent and a gas flow method as shown below is preferred. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Among them, the oxidation method accompanying the gas flow uses nitric acid as the oxidant. In this high-speed gas flow, the carbon black is at an appropriate temperature. After the next oxidation, one of the manufacturing steps to separate nitrogen oxides from carbon oxides is a novel oxidation method that can uniformly mix the higher volatile components of carbon black. In more detail, a gas containing nitric acid gas of 1 vol% or more and 30 vol% or less, more preferably 2 vol% or more and 15 vol% or less, is passed at 3 m / s or more, and more preferably 5 m / s or more. In the flow rate, the nitric acid in the gas disperses carbon black before the nitrogen dioxide is decomposed, and the carbon black is transferred to the reaction device in a gas stream. At that time, the ratio of the weight of nitric acid gas contained in a unit volume of gas to the weight of the carbon black dispersed in the gas (the ratio of nitric acid / carbon black) is the final carbon paper. The Chinese national standard (CNS) A4 specification (210X297)嫠) .Q〇- 536551 A7 B7_ 5. Description of the invention (88) Important factor of black volatile content. That is, in order to impart a larger amount of volatile components, the ratio of nitric acid / carbon black can be increased. In order to achieve the above-mentioned concentration of nitric acid gas, heating, ultrasound and other methods can be used to increase the degree of nitric acid gas in the gas phase. ^ Nitrogen-containing gas that can react with carbon black. In addition to nitric acid, inert gas such as air or nitrogen can be used. Raw materials can be nitric acid or gas obtained by water vapor containing water in the air. The components such as nitric acid water vapor containing this mixed gas are introduced under the pre-heating temperature at the temperature before being completely condensed, and are introduced in a heat-preserving state or a heating state in which the temperature is not reduced during the introduction. However, when the temperature of the nitric acid gas is too high, it will rapidly decompose into nitrogen dioxide. Therefore, the temperature of the mixed gas in contact with the carbon black is preferably in the range of 50 ° C to 200 ° C. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Carbon blacks usually co-aggregate with each other when they are collected in the collection bag, resulting in weak agglutination of thousands to nm. State, if it is introduced into the gas stream in this condensed state during the oxidation reaction, it will settle in the device and cause adhesion inside the device, or the local concentration of carbon black in the condensed part and the non-condensed part will be different, resulting in The uneven concentration of local nitric acid / carbon black is also the cause of the uneven concentration of carbon black produced. For carbon black with weak cohesiveness and low volume specific gravity, if carbon black is simply mixed into the aforementioned high-speed airflow, it will be crushed by the energy of the airflow and can be oxidized in a uniform concentration state. However, for carbon black with a higher volume specific gravity, it will not be fully decomposed in the energy of the air flow of 3 m / s to 5 m / s, but in order to obtain a better dispersed state of carbon black, various A gas phase decomposition device or a pulverizer is preferred. The device set up for this purpose applies the Chinese National Standard (CNS) A4 specification (210X297 cm) -91-536551 A7 B7 to the paper size of the present invention. V. Description of the invention (89) The implementation device is most likely to implement a small size The device is a kind of device that can utilize the pressure of high-speed airflow, and only make the part of the carbon black gas flow more high-speed. It can be accelerated to more than 2 Om / second, and more preferably 5 Om / second. When the carbon black phase supplied by the device strikes,% ... provides a spray dispersion device with extremely high crushing energy in an instant. This nitric acid-containing gas and carbon black are strongly mixed by the energy of a high-speed gas stream. If the reaction environment is maintained at a temperature of 50 t or more that can effectively cause an oxidation reaction, and the functional group that can be inhibited by the oxidation reaction is suppressed In a temperature state below 250 ° C where thermal decomposition occurs, it is preferable to perform the reaction within 10 seconds to 600 seconds in order to make full use of the oxidation reaction generated by nitric acid. In order to obtain a carbon black with a high volatile component / N 2 S A ratio, the temperature of the oxidation reaction region is preferably suppressed to a temperature of 120 ° C to 200 ° C. Among them, a device for maintaining carbon black at a certain temperature range in a certain flow rate range is used to use a double-tube reaction device having an indirect temperature control function. ~ Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). During the reaction, the acid gas can be mixed into the gas stream during the reaction to compensate for the initial consumption of nitric acid. Thereafter, by-products obtained by the reaction of nitric acid, such as nitrogen oxide gas containing nitrogen dioxide, nitrogen monoxide and the like, are separated from the oxidized carbon black. Various methods can be used to separate the gas from carbon oxide black after the reaction. For example, a cyclone separator, such as a classification device that can change the powder conveying capacity, or a collection bag to change the collection method, can be used, but in order to make fine particles completely For separation in gas, it is better to use a trap screen to collect and separate it. The surface of the device used at this time shall be made of acid-resistant and paper-resistant paper that conforms to the Chinese National Standard (CNS) A4 (210X297 mm) -92 · 536551 A7 B7 V. Description of the invention (90) Nitrogen oxide reinforced glass fiber The obtained furnace cloth is more preferable because it can improve the durability. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Carbon black with a reaction time of 10 to 600 seconds after the reaction has passed. In the case of dioxin-nitrogen or unreacted ceremonies, these substances react with carbon atoms on the surface of carbon black when the temperature rises and the heat is generated rapidly. Therefore, when the oxidized oxidized carbon black is recovered by a bag filter, the accumulation and capture part of the carbon black obtained from the separation from the gas has a lower exothermic efficiency than that in the air flow part, so the carbon black can be generated when the reaction generates heat. As the temperature increases, once the functional groups attached to the surface are decomposed and detached, the activation reaction caused by the reaction between nitrogen oxides and carbon black at high temperature increases the specific surface area. If the temperature is higher, combustion will occur and the carbon black will disappear. When studying this phenomenon, we know that the reason is that the exothermic reaction occurs when the temperature of the carbon black reaches 110 ° C or higher, and it violently progresses above 120 ° C. In particular, when oxidation with volatile components of more than 7% by weight, if the temperature of the carbon black in the accumulation state is above 120 ° C, the temperature of the carbon black will increase in a chain, and some or all of the carbon black will be blocked. Suitability, and then reach a temperature above 200 ° C in a short time. In order to avoid this rapid temperature rise, the indirect heat exchange temperature adjustment device installed in the collection bag part or the temperature adjustment device that can directly eject cold gas is used to control to 1 2 0 ° C or lower, preferably 100 ° C or lower. In order for this carbon black to absorb more nitrogen oxides, the carbon black needs to have a detachment device that can control the temperature within 50 ° C above and below the set temperature so that the carbon black can contact the gas inside the device during the flow. , Heating at a temperature of 120 ° C or higher, preferably 150 ° C or higher, and 200 ° C or lower, and the paper size applies the Chinese National Standard (CNS) A4 grid (210X297 mm) -93- 536551 A7 B7 V. Description of the invention (91). The amount of nitrogen-containing oxides is kept below 2000 p pm, preferably below 1 ο 〇p pm for 5 minutes to 60 minutes, and it can be adsorbed on the surface of carbon black. Nitrogen oxides are hardly detached to form harmful nitric acidic carbon black f. Using the above method, a unit surface area with a higher -volatile content, smaller particle size, and a specific surface area of N 2 SA / SE M can be obtained. Carbon black with small specific ratio, small ratio of iodine adhesion / nitrogen adhesion specific surface area (N 2 SA), c DB P can be set to a certain range, and carbon black with this characteristic can be used to obtain Widely dispersed carbon black composition with high darkness. That is, the following methods are used. (1) A method for producing acidic carbon black, which is to contact and mix carbon black with nitric acid gas in a state where the carbon black is dispersed with the energy of the air stream in a gas stream containing nitric acid. (2) — A method for producing acidic carbon black, which is obtained by separating the acidic carbon black obtained in accordance with the method (1) above from the nitrogen oxide-containing gas at 100 ° C to 200 ° C. The nitrogen oxides adsorbed on carbon black are separated at a temperature of ° C. ~ Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (3) In the manufacturing method described in (2) above, carbon black and nitrogen oxides are separated by a bag filter. (4) In the manufacturing method of any one of (1) to (3) above, the temperature of the gas stream containing the nitric acid gas is maintained between 50 ° C and 200 ° C until the carbon black oxidation reaction is completed. (5) In the manufacturing method of any one of (1) to (3) above, the temperature of the gas flow of the nitric acid-containing gas in which the carbon black is dispersed is maintained at a temperature of 120 ° C to 200 ° C. -94- (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 ____B7____ 5. Description of the invention) (6) The above (1) In any one of the production methods) to (3), the temperature of the gas flow of the nitric acid-containing gas in which the carbon black is dispersed is maintained at a temperature of 50 ° C to 150 ° C. (7) In the manufacturing method of any one of the above (1) to (3), the temperature of the gas flow of the nitric acid-containing gas in which the carbon black is dispersed is maintained between 50 ° C and 130 ° C. (8) In the manufacturing method of any one of (1) to (7) above, the contact time between the air flow and the carbon black is between 10 and 600 seconds, and preferably between 10 and 120 seconds. (9) In the manufacturing method of the above (3), the temperature of a part of the bag filter is controlled to 12 0 t: or less. (1 0) — A method for controlling the quality of carbon black, which is controlled by changing the ratio of the concentration of nitric acid in the air stream to the concentration of carbon black in the manufacturing method of (1) to (8) above. Brief Description of the Drawings Fig. 1 ... An illustration of an example of the carbon black manufacturing apparatus of the present invention. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Figure 2 ... Illustration of the angle of the choke inlet in the carbon black manufacturing device of the present invention. Figure 3 ... An example of the change in turbulent energy. Figure 4 ... A schematic diagram of a combustion chamber with a cooling structure used in Example 4 9 ~ 5 1 Figure 5 ... Calculating the maximum frequency Stokes equivalent particle size Dmod and the maximum frequency Stokes equivalent particle size D i The ratio of / 2 is an example. -95- (Please read the notes on the back before filling in this page) The paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) 536551 A7 B7__ V. Detailed description of the invention Figure 6 ... Calculate volume 75 Illustration of% (D75). Fig. 7 ... Longitudinal section of important parts exemplified by the carbon black manufacturing apparatus of the present invention 槪 I ○ Fig. 8 ... Example of a manufacturing furnace which can be used when producing carbon black in the present invention-Example 2: Longitudinal section of important parts 槪 Schematic view. Figure 9 ... Section A_A in Figure 8. Fig. 10 ... A calculation model diagram used in Example 55. Figure 1 1 ... Computational model diagram of Comparative Example 4 4. Figure 1 2 ... A schematic diagram of a carbon black manufacturing device used in Examples 6 2 to 64. Fig. 1 ... The carbon black production equipment used in Comparative Examples 4 6 to 48 is a schematic diagram. Figure 1 4 ... Comparative Examples 4 9 to 5 1 Carbon black manufacturing equipment 槪 Outline drawings. Figure 15 ... is a calculation model diagram for calculating the heat transfer degree in a carbon black manufacturing furnace. Figure 1 6… Measured by the temperature measurement at point A, the temperature of the furnace wall and the gas temperature in the furnace are printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Fig. 17 ... Diagrams of the temperature inside the furnace and the temperature of the gas in the furnace from the temperature measurement at point B. Fig. 18 ... A schematic drawing of a longitudinal section of an important part exemplified by a manufacturing furnace which can be used in the production of carbon black in the present invention. Fig. 19 is a schematic view of a co-current type gas oxidation reaction device used in Example 72. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -96--536551 A7 B7 V. Description of the invention (94) Figure 2 0 ... Figure 1 19 The supply / dispersion of carbon black Sketch of the device. Figure 2 1 ... The release device used in Example 72. ^ [Illustration of symbols of main components in the figure] Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1 The first reaction zone 2 The second reaction zone 2 a Front part of the choke tube 2 b Rear part of the choke tube 3 The third reaction zone 1¾ 4 Gas choke section 5 Combustion nozzle 6 Hydrocarbon raw material introduction nozzle 7 Reaction stop fluid introduction nozzle 8 Control valve 9 Gas choke section □ section ~~ 1 0 Gas choke section 1 1 Fuel gas flow 1 2 Gas choke section section □ Angle 1 3 Furnace wall 2 1 Cooling jacket 2 2 Cooling medium inlet □ Nozzle 2 3 Cooling medium outlet □ Nozzle 2 4 Atomizing section (please read the precautions on the back before filling this page) This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) -97- 536551 A7 B7 V. Description of the invention (95 2 4-1 convex part 2 4-2 m / Viw burning gas spray hole 2 4-3 help fyiw gas introduction hole 2 5 Flange 2 6 〇 ring 2 7 Set screw 2 8 Reed for fixing the atomizer 2 9 Fuel introduction hole 2 10 m riiw Material introduction flange 2 11 Assist r〇 \\\ Gas introduction nozzle 3 0 Carbon black supply / dispersion (please read the note on the back first) Please fill in this page again) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 3 3 3 3 3 3 2 3 4 5 6 7 8 3 12 3 Jet Disperser Thermostatic Tank Reaction Tube Heater Cylinder Nitric Acid Dosing Pump Air Compressor Separation device Hot air hopper Feeder Dosing device Sprayer Gas nozzle The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 98- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 536551 A7 __; __B7 V. Description of the invention (96) 3 9 0 Cylindrical part 3 9 2 Heating air supply port 3 9 3 Into □ screen 3 9 4 Out □ screen 3 9 5 Below the body exhaust port, the present invention will be described in more detail with examples. (Example 1 &lt; 4) as shown in FIG. 1, a first reaction zone region having an inner diameter of 50 mm in air and a length of 140 mm in order of the air introduction duct and the combustion chamber is provided, and is connected to the first reaction zone area, and A second reaction zone region having an inner diameter of 6 Omm and a length of 80 mm and a choke tube portion provided with a plurality of raw material nozzles passing through the periphery, and a third reaction zone region with an inner diameter of 100 mm and a length of 600 mm , And a carbon black manufacturing furnace consisting of a control valve with a narrow mechanism with an inner flap diameter of 80 mm. The position of the raw material nozzle is 100 mm from the entrance of the choke tube part. Using the manufacturing furnace described above, carbon black was manufactured under the conditions shown in Table-1. The fuel and the hydrocarbon raw materials are dyed phenol oil. In Examples 3 and 4, oxygen may be added to the air to increase the temperature of the combustion gas. In the table, "combustion gas temperature", "combustion gas oxygen concentration" and "furnace pressure" are the values measured for the introduction of hydrocarbon raw materials. "Potassium concentration" refers to the concentration of K Η added to the hydrocarbon raw materials, and the Chinese national standard (CNS) A4 specification (210 × 297 mm) is applicable to the paper standard of potassium concentration -99- -------- -·! (Please read the precautions on the back before filling out this page) Order 536551 A7 B7 _ V. Description of the invention (97) · Degree mode specification. Various characteristics of the obtained carbon black are shown in Table-2. The analysis method of the obtained carbon black is measured according to the following experimental methods: (Specific surface area) The specific surface area (N2SA) is determined according to ASTM D3037 -8 8 (c DBP) The broken DBP absorption coefficient (cDBP) is according to ASTM D 3 Determination of 4 9 3 — 8 8 (Dmod, D 1/2) The half-width of the maximum frequency Stox equivalent particle size (Dm〇d) and the maximum frequency Stox equivalent particle size (D i / 2) It is determined as follows. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Use a 20% ethanol solution as the spin solution, and use a centrifugal sedimentation flow distribution measurement device (manufactured by JK Audemei) DCF 3) Measure the Stokers equivalent particle size, and make a frequency diagram of the relative frequency for samples with Stokers equivalent particle size (Figure 1-5). The wave graph (A) of the frequency diagram is stretched toward the line (B) and parallel to the Y axis to the X axis, and ends at the point (C) of the X axis in the frequency diagram. The Stokes diameter at point (C) is the maximum frequency Stokes equivalent particle size DmOd. The midpoint (F) of the measurement line (B) is drawn through the midpoint (F) so as to be parallel to the X axis. Line (G) intersects the distribution curve of the frequency diagram at two points D and E. Carbon black particles The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm).-| 〇〇. &Quot; &quot; 536551 A7 __B7_ V. Description of the invention (98,). 2 points D and E The absolute value of the difference from the diameter of the two Stakekes is half the size of the Stakekes equivalent particle size D 1/2 値. ------ (D 7 5). One volume 7 5% diameter (D75) is determined in the following way. According to the method of the maximum frequency Stokes particle size determined by the above, the volume of the Stokes equivalent particle size versus the relative frequency of occurrence of the sample is shown in Fig. 5. The respective Stokes diameter and frequency are used to calculate the volume. The graph of the total volume of the tux diameter and the diameter of the metal product (Figure 6). The point (A) in Figure 6 is the sum of the total sample volume. Here, the point (B) of 75% of the total volume is determined, and a line intersecting the curve is drawn from the point (B) in a parallel X-axis manner. A line is stretched from point (C) in parallel to the Y axis, and the point (D) where it intersects the X axis is the volume 75% diameter (D 7 5) 0 (PVC blackness)… Central Standards Bureau of the Ministry of Economic Affairs The PV c blackness printed by the employee consumer cooperative is the carbon black of the present invention added to the PVC resin, dispersed with a double roller to make it flake, and the carbon black of Mitsubishi Chemical Corporation "# 40" '"# 45" The blackness is set to a standard of 1 point and 10 points, and the blackness of the sample is judged visually. (Dispersion Index) The dispersion index is evaluated according to the following method. Observe the dispersion in L d PE resin and calculate the number of undispersed agglomerates. If this number is -101-(Please read the precautions on the back before filling this page) The paper size applies to Chinese National Standard (CNS) A4 Specifications (210x297 male thin) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 536551 A7 B7 V. Invention Description (99) For a long time, that is, the dispersion index is large and the dispersion is not good. The carbon black sample was added to the LDPE resin at a weight of 40% in a 2 500 cc spotbury kneader, and the mixture was kneaded at 1 15 ° C for 1 minute. The conditions were 101.89 g of calcium stearate LDPE 1 3 9 g Enox 1010 0.87g carbon black sample 6 9. 4 3 g Secondly, the carbon black concentration was diluted to 1% by weight at 120 ° C, double roller mixing. Preparation conditions for the diluted composition: 58.3 g of LDPE resin, 0.2 g of calcium stearate, 0.2 g of carbon black containing 40% by weight of resin, 1.5 g, and sheeting with a slit width of 0.3 mm. A 6 5 ± 3 // m film was made on a hot platen at 240 ° C. The diameter of the non-dispersed aggregates with a diameter of 0. 2 mm or more was measured in a field of view of 3 · 6mm × 4 · 7mm at a magnification of 20 times and the total area was calculated. This area is based on the area of the undispersed aggregates with a diameter of 0.35 mm, the total area is divided by the reference area, and the number of reference particles is calculated. This was observed in a visual field of 16 or more, and the average 値 was used as a dispersion index. The productivity of the same particle size or the same blackness of the PVC can be applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) for this paper size. 10 2 ---------- AW ----- -'玎 ------ (Please read the notes on the back before filling out this page} 536551 A7 B7 V. Description of the invention (100) Feed supply X Raw oil production / air volume indication. And' Fuel of The consumption ratio decreases with the increase of the total carbon production. (1) The particle size is measured by the electron microscope method. The electron microscope method is the method described below. Carbon black is put into chloroform and irradiated with 2 0 OKH Z 2 After dispersing for 0 minutes, the dispersed sample was fixed with a support film. It was photographed with a transmission electron microscope, and its particle size was calculated by the diameter on the photo and the magnification of the photo. This operation was performed for about 150 seconds. 〇, and use the arithmetic average as the measurement 値 (Please read the notes on the back before filling in this page) Printed paper size of the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, the paper size applies to China National Standard (CNS) 8 4 specifications (210X297 Mm) · 103-536551 B7 V. Invention theory (101) Printed Table 1 by the Central and Associate Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Fuel kg / H 54 5 2--54 58 5 2-5 4 Air volume Nm3 / H 520 500 470 480 500 529 (13) (20) (22) (19) Temperature of combustion gas ° c 1821 1820 1920 2090 1785 1810 Oxygen concentration of combustion gas% 0.06 0.04 0.39 0.58 4.44 5.52 Combustion gas Gas blocking tube section 390 378 375 408 384 329 Flow rate m / s Feedstock supply Kg / H 55 53 59 62 65 59 Pressure in the furnace kg / cm3 0.54 0.57 0.62 0.65 0.58 0.50 Potassium concentration ppm 0 800 800 800 0 800 Time msec 2.05 2.11 2.14 1.96 2.08 1.28 (Please read the precautions on the back before filling out this page) (The flow rate of the added oxygen) This paper size is applicable to China National Standard (CNS) Α4 size (2l0x297 mm) -104- 536551 A7B7 V. Description of the invention (102) Table 1 2 Example 1 Example 2 Example 3 Example 4 Comparative example Γ Comparative example 2 Particle size nm 15 15 -1-2 11 17--15 N2SA m2 / g 262 248 320 360 193 271 cDBP cc / 1 00g 103 64 67 68 99 65 D m 0 d nm 43 32 29 25 68 35 D 1/2 nm 24 19 17 15 35 21 D75 nm 53 41 37 31 95 85 D75 / Dmod 1.23 1.28 1.27 1.25 1.40 2.43 pvc blackness index 16.3 19.3 30.0 32.0 8.0 18.0 dispersion index index 20 120 125 130 40 175% of feedstock oil production rate 63.6 65.4 61.3 66.2 37.2 45.6% of total carbon yield 32.1 3 3.0 32.0 34.2 19.0 18.6 D 1/2 / D m od 0.558 0.594 0.586 0.6 0.515 0.6 (please first- (Please read the notes on the back of M. Please fill in this page again.) (Comparative Examples 1 and 2) The Carbon Black Manufacturing Furnace used in the Example was printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, and Comparative Example 1 was implemented under the conditions of Table-1. Comparative Example 2 is a manufacturing furnace in which the length of the choke tube portion of the manufacturing furnace of the example was 500 mm. The physical properties of the obtained carbon black are shown in Table-2. When the carbon black obtained in the example is compared with the carbon black obtained in the comparative example, as shown in Table-2, the example has a smaller particle size than the comparative example. In addition, when comparing Examples 1 and 2 with Comparative Example 2, although the particle size is the same as the standard paper size, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied-105-536551 A7 B7___ V. Description of the invention (103) · Same, but the yield of the raw material oil and the total carbon yield of the examples are greatly improved. (Please read the precautions on the back before filling in this page.) In addition, Example 1 and 2 are smaller than Comparative Example 2 1/2 / Dmod and the distribution of the aggregate diameter is more concentrated, and D75 値 is also smaller, so large aggregation There is less material in the i-path. In addition, it exhibits a high degree of blackness, and the -dispersion index is also low, and the degree of dispersion is good. (Examples 5 to 9 and Comparative Examples 3 to 4) Using the manufacturing furnaces of Examples 1 to 4, the carbon black described in Table 1 4 was prepared according to the conditions in Table 1 3. In Table 1, 3, the "flow rate of combustion gas" refers to the flow rate in the choke tube. As shown in Table 1, when Comparative Example 3 is compared with Examples 5-9, D i / 2 / Dm0d is large, the blackness is low, the dispersion index is high, and the dispersibility is deteriorated. Moreover, the specific surface area N 2 S A of Comparative Example 4 was small, the particle size was large, and the blackness was low. (Comparative example 5) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The obtained carbon black was placed in a choke tube with a diameter of 50 nm and a choke tube flow velocity of 105 m / s, and a choke tube with a flow velocity of 2 The cases of 50 m / s' choke tube diameter 180 mm were compared with Comparative Example 5 and Comparative Example 4 individually. As shown in Table 1, when Comparative Example 5 is compared with Examples 1 to 10, D 1/2 / Dmod is large, the dispersion index is high, and the dispersibility is deteriorated. In addition, the specific surface area of Comparative Example 4 is small N 2 S A ′, the particle size is large, and the blackness is low. The paper size is in accordance with China National Standard (CNS) 8-4 specification (210 X 2W mm) -106- 536551

7 7 A B V. Description of the invention (104) Table 1 3 _ Fuel kg / h Air volume Nm2 / h Temperature of combustion gas. C Oxygen concentration of the combustion gas dr-y-vol% Flow velocity of the combustion gas m / s Feedstock quantity kg / h- Example 5 61 586 1622 0.6 336 82 Example 6 58 531 177 7 0.1 435 77 Example 7 61 573 1780 0.2 358 82 Example 8 56 535 1756 0.5 391 99 Example 9 56 535 1748 0.5 391 97 Comparative Example 3 10.1 98 1642 0.2 80 14 Comparative Example 4 310 3000 1777 0.1 250 435 Comparative Example 5 16 150 1622 0.6 105 21 ( Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, Table 1 3 (continued) Pressure in the furnace kg / c m2 G Gen concentration ppm Gas choke diameter mm Turbulent mixing speed 1 / s Example 5 1.0 0 50 502 Example 6 0.5 0 50 646 Example 7 1.0 0 50 535 Example 8 0.7 98 50 535 Example 9 0.7 495 50 585 Comparative Example 3 0.4 0 50 117 Comparative Example 4 0.3 0 180 117 Comparative Example 5 0.5 0 50 This paper is sized according to the Chinese National Standard (CNS) A4 (210X297 mm)-107-536551

7 7 A B V. Description of the invention (105) The turbulent mixing speed in the table refers to the maximum 値 on the central axis in the choke tube. Also, the mathematical calculation system uses a binary axisymmetric model. Table 1 N2S Am2 / g CrDBP ml / 1 00g D m 0 d nm D1 / 2 nm D1 / 2 / D m 0 d PVC Blackness Score Index Example 5 120 90 70 33 0.47 4.7 11 Example 6 128 93 68 34 0.5 5.7 13 Example 7 '132 94 66 35 0.53 4.7 15 Example 8 112 77 68 35 0.52 5.7 28 Example 9 121 59 60 30 0.5 8.0 78 Comparative Example 3 101 88 87 63 0.72 1.0 18 Comparative Example 4 110 91 80 44 0.55 2.0 20 Comparative example 5 122 88 73 58 0.79 3.3 85 (Please read the notes on the back before filling out this page) (Comparative example) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, mixing the turbulent mixing speed to 1 1 The case of 7 / s (the choke tube diameter of 50 nm and the choke tube flow velocity of 80 m. / S, and the choke tube with a flow velocity of 250 m / s and choke tube diameter of 180 mm) are used as a comparison. Example 3 and Comparative Example 4. Other conditions were the same as in Example 5 to produce carbon black. The physical properties of the obtained carbon black are shown in Table-4. (Example 1 0 to 1 3) The inner diameter of the air inlet duct and the combustion chamber is sequentially connected to 50 0 -108- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7 V. Description of the Invention The first reaction zone area of (106) mm, a length of 1400 mm, and the periphery connected to the first reaction zone area are penetrated by a plurality of raw material nozzles having an inner diameter of 60 mm and a length of 800 mm formed by a gas choke tube portion. 2 reaction zone ^, and a third reaction zone with an inner diameter of 100 mm with a cooling device, a length of 6 0 0 m πν, and a control valve with a narrow mechanism with an inner valve diameter of 80 mm The constructed carbon black manufacturing device. (Example 1 4) A cone-shaped carbon black manufacturing device with an inner diameter of 50 mm at the inlet and an inner diameter of 100 mm at the outlet of the choke tube portion was provided in Examples 1 to 13. Each of the manufacturing equipment of 14 uses phenolic oil as the fuel and hydrocarbon raw materials, and produces carbon black under the conditions shown in Table-5. Various characteristics of the obtained carbon black are described in Table-6. The test method for carbon black produced according to the present invention uses the method described above. (Comparative Examples 6 to 9) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Use the manufacturing furnace used in the example, where the length of the choke tube section is changed to 500mm The carbon blacks of Comparative Examples 6 and 7 were manufactured under the conditions shown in Table 5 and their physical properties are shown in Table-6. Also Comparative Example 8 and Comparative Example 9 are physical properties of carbon blacks "# 9 9 0" and "# 9 6 0" sold by Mitsubishi Chemical Corporation. When the carbon black of Benming was used for comparison with the comparative example, as shown in Table 1, in Comparative Example 6 and Comparative Example 7, from the beginning of the spraying of the raw material oil to the substantial disruption of the paper size, the Chinese National Standard (CNS) A4 specification was applied ( 210X297 male thin 1 7-109. &Quot; Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 536551 A7 ___ B7 V. Description of the invention (107) (to the extent that the airflow shown in Figure 3 cannot be ignored) Since the time is less than 1.5 ms, the generation of aggregates with large particle sizes cannot be suppressed. Therefore, when the carbon black obtained in the example is compared with the comparative example, D Π 2 / Dmod is smaller and the distribution of the aggregate diameter is more Concentration, D 7 5 値 is also smaller, and there is less material with large aggregate diameter. Also, it exhibits high blackness, and the dispersion index is also low, and the dispersion is good. ---------- ------ IT ------ Awl (Please read the precautions on the back before filling out this page) Table 1 5 Fuel kg / h Air mL Nm2 / h Combustion gas temperature ° C Combustion gas oxygen Concentration% Velocity in the choke tube of the combustion gas m / s Feed amount kg / h Example 10 53 530 1622 0.65 356 100 Example 11 52 500 1785 0.04 368 65 Example 1 2 54 530 1748 0.46 383 80 Example 13 54 520 1821 0.06 390 55 Example 14 78 750 1840 0.04 374 (* 1) 80 Comparative Example 6 52 520 1625 0.65 353 85 Comparative Example 7 52 500 1770 0.04 369 70 (* 1) The average flow velocity in the choke tube. -110- 536551

7 7 AB Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (108) Table 1 5 (continued) Pressure in the furnace kgf / cm2G Potassium concentration ppm The entrance of the choke tube section until the spraying of the raw oil-the ... time ms raw material Time from oil spray to large disturbance ms Obstacle tube diameter mm Example 10 0.60 0 0.28 1.97 60 Example 11 0.58 0 0.27 1.9 60 Example 12 0.58 495 0.26 1.83 60 Example 1 3 0.54 0 0.26 1.80 60 Example 14 0.62 800 0.15 2.19 Inlet 50 Outlet 100 Comparative Example 6 0.45 80 0.28 1.13 60 Comparative Example 7 0.42 0 0.27 1.08 60 (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) -111-536551 A7B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (109) Table 1 6 _ Particle size nm N2SA m2 / g CrDBP cc / 100g D m 0 d nm Dl / 2 nm D75 nm Dm / D m 0 d Example 10 24 120 90 -Ί-0 3 3 86--0.471 Example 11 17 193 99 68 35 82 0.515 Example 12 20 163 74 40 23 49 0.575 Example 1 3 15 262 103 43 24 53 0.558 Example 14 15 260 70 33 20 43 0.606 Comparative Example 6 23 130 96 68 4 2 124 0.618 Comparative Example 7 19 175 85 57 35 93 0.614 Comparative Example 8 15 240 82 44 37 67 0.841 Comparative Example 9 15 240 60 44 37 75 0.841 Table —6 (continued) D75 / Dmod PVC blackness index dispersion index index Example 1 1.23 5.3 10 Example 2 1.20 8.0 15 Example 3 1.23 12.3 40 Example 4 1.23 16.3 20 Example 5 1.30 18 80 Comparative Example 1 1.82 6.3 20 Comparative Example 2 1.63 8.0 30 Comparative Example 3 1.52 16.7 40 Comparative Example 4 1.70 18.3 180 (Please read the notes on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)- 112 · 536551 A7 B7 Five 'invention description (110). (Example 1 5 ~ 1 8) According to the sketch shown in Fig. 1, sequentially connect the first reaction zone area with the air introduction duct and the combustion chamber, and The second reaction zone area formed by the choke tube section with an inner diameter 6 of a plurality of raw material nozzles and a length of 1 0-0 mm is connected to the periphery of the first reaction zone area, and the inner diameter of the cooling device is 100 mm. Carbon formed by the third reaction zone area of 6 000 mm in length Manufacturing furnace. The position of the raw material nozzle is 100 mm from the entrance of the choke tube part. Using the above-mentioned manufacturing furnace, the temperature of the combustion gas, the oxygen concentration of the combustion gas, the supply amount of the raw material, etc. were adjusted at the position where the hydrocarbon raw material was introduced to produce carbon black having physical properties as shown in Table-7. Fuel and hydrocarbon raw materials are dyed phenol oil. The air introduced into the area of the first reaction zone is the air with oxygen added through the air duct, and the introduction position of the hydrocarbon raw material is maintained at a high temperature environment of more than 1 900 t. In the table, the positive heat-resistant aging time of the S EM specific surface is calculated by the following method. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (S EM specific surface area) S EM specific surface area is calculated according to the following formula. SEM = 6000 / (p * dA) Specific gravity of carbon black (1.86g / cm3) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm &gt; Γΐ13- 536551 A7 B7 V. Description of the invention (111 ) dA = (particles) body area diameter (nm) (heat-resistant aging time) ~ The heat-resistant aging time is evaluated in the following way.. Carbon black is added to the dispersant (magnesium stearate) at 40% and mixed. Grind and mix for 10 minutes with a household blender to make dry granules. Secondly, add the aforementioned dry granules (carbon black 0.5%) to the polypropylene powder granules, and then use a Banbury mixer at 1 4 Knead for 20 minutes at 0 ° C, and flake at 170 ° C with a biaxial roller mill. Model temperature 220 °, molding pressure 100 jerk {/ (: 1112-2 2 111111 thickness Flat plate press molding. Five test samples prepared in this way were placed in a gear oven set at 150 ° C for 285 hours to determine the heat-resistant aging time. It was visually judged that the surface began to turn white The time is the heat-resistant aging time. (Comparative Examples 10 to 1 3) ^ Example printed and used by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs In the carbon black manufacturing furnace used, the temperature of the combustion gas, the reaction stop position, the amount of potassium addition, the gas flow rate in the choke tube, etc. are adjusted at the introduction position of the hydrocarbon raw material to produce a comparative example 10 shown in Table-7. The physical properties of carbon black. Comparative Examples 1 to 13 are the physical properties of commercially available carbon black. When comparing each example with Comparative Example 1, the Examples have a higher degree of PVC blackness than Comparative Example 10. This point should be This is because the particle size of Comparative Example 1 is outside the range specified in the first invention of this invention. -114- (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 5 5 6 3 f Β7 V. Description of the invention (112) When each example is compared with Comparative Example 11, Comparative Example 11 has a shorter heat-resistant aging time than the Example. This point should be p Η故 Because it is outside the range specified in the first invention of the present invention. &Gt; Compared with Comparative Examples 3 and 4 in each example, the dispersion indices of Comparative Examples 1 2 and 13 are large and the dispersion degrees are not good. This is because the D! / 2 / Dm〇d of Comparative Examples 1 2 and 1 3 are 0.71 and 0.68 respectively, and The reason is beyond the scope of the first invention. Table 1 7 Particle size N2SA D1 / 2 D m 0 d D1 / 2 / D75 D75 / nm m2 / g nm nm D m 0 d nm Γ) mod Example 15 12 320 17 29 0.586 37 1.27 Example 16 11 360 15 25 0.6 31 1.24 Example 17 10.1 520 15 32 0.47 39 1.22 Example 18 8.3 694 11 26 0.423 41 1.58 Comparative Example 10 17 193 35 68 0.515 82 1.21 Comparative Example 11 13 550 25 45 0.556 64 1,42 Comparative example 12 15 300 22 31 0.71 165 5.32 Comparative example 13 13 350 21 31 0.677 211 6.81 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy -115- (Please read the precautions on the back before (Fill in this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7B7 (Example 1 9 ~ 2 2) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (113) Form 7 (continued) Cdbp pH PVC blackness dispersion heat resistance cc / 100g 100 index m ΓβΙ hr Example 15 67 6.5 -30-- 125 28 «Above Example 16 68 6.8 32 130 280 Above Example 17 110 5.9 28 55 280 above Examples 18 110 6.2 33 8 5 280 or more Comparative Example 10 99 6.6 8 15 280 or more Comparative Example 11. 97 2.0 27 55 144 Comparative Example 12 44 6.5 29 720 Comparative Example 13 49 6.0 29 430. 雠 (Please read the precautions on the back before filling this page) Using the manufacturing furnaces of Examples 15 to 18, the temperature of the combustion gas, the oxygen concentration of the combustion gas, and the supply amount of the raw materials were adjusted at the hydrocarbon material introduction position to produce carbon black having physical properties as shown in Table-8. Phenol oil is used as the fuel and hydrocarbon raw materials. The air introduced into the area of the first reaction zone is the air with oxygen added through the air duct, and the position of the introduction of hydrocarbon raw materials is maintained at a high temperature environment above 1 900 ° C. In the table, T% is measured by the following method. (T%) Toluene tinting power (T%) is determined in accordance with ASTM D-1618-83. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) · 剠 6 · 536551 A7 B7___ V. Description of the invention (114) (Comparative Examples 1 4 to 16) The carbon black manufacturing furnace used in the examples At the introduction position of the original hydrocarbon, adjust the temperature of the combustion gas, the stop position of the reaction, the potassium addition force, the amount of gas, and the gas flow rate in the choke tube to produce Comparative Examples 1 to 4 as shown in Table-8. Physical black. In addition, Comparative Example 16 is a physical property of a commercially available carbon black. When each example is compared with Comparative Example 14, the Example has a higher blackness than that of Comparative Example 14. This is because the particle diameter of Comparative Example 14 is outside the range specified in the second invention of the present invention. When each example is compared with Comparative Example 15, the examples have a higher T% T. This should be because the proportion of unreacted polycyclic aromatic hydrocarbons in carbon black is low, which means that the safety of carbon black is high. This point should be the ratio of N2 SA / S EM in Comparative Example 15 (beyond the range specified in the second invention of the present invention), and also shows the ratio of N2SA / S EM to the ratio of unreacted polycyclic aromatic hydrocarbons Relevant. ~ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). When comparing each example with Comparative Example 16, Comparative Example 16 has a shorter heat aging time than the Example. This is because p Η 値 is outside the range specified in the second invention of the present invention. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -117 · 536551 A7B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (115) Table 1 8 Particle size N2SA SEM N2SA D1 / 2 D m 0 d D1 / 2 / D75 nm m2 / g m2 / g / SEM nm nm D m 0 d nm Example 1 9 12 320 218 1.47 • -17 29 0.586- 37 Example 20 11 360 240 1.50 15 25 0.6 31 Example 2 1 10.1 520 278 1.87 15 32 0.47 39 Example 22 8.3 694 313 2.2 11 26 0.423 41 Comparative Example 1 4 17 193 170 1.13 35 68 0.515 82 Comparative Example 1 5 11 301 235 1.28 17 26 0.654 63 Comparative Example 1 6 13 550 262 2.1 25 45 0.556 64 (Please read the precautions on the back before filling this page) Table 1 8 (continued) D75 / cDBP pH 値 T% PVC dispersion heat aging ID m 0 d cc / 1OOg Blackness index Time hr Example 19 1.27 67 6.5 99 3 0 125 280 or more Example 20 1.24 68 6.8 99 32 130 280 or more Example 2 1 1.22 no. 5.9 98 28 55 280 or more Example 22 1.58 110 6.2 99 33 85 280 or more Example 14 1.21 99 6.6 97 8 15 280 or more Comparative Example 1 5 2.42 70 7.1 65 30 260 280 or more Comparative Example 1 6 1.42 97 2.0 99 27 55 144 (Example 2 3 to 2 6) Using the manufacturing furnace of Examples 1 5 to 18, the temperature and combustion of the combustion gas were adjusted at the hydrocarbon feedstock introduction position. The oxygen concentration of the gas and the raw materials for this paper are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -118-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 536551 A7 B7 5. Description of the invention (116). The amount is equal to produce carbon black having physical properties as shown in Table 1-9. Phenol oil is used as the fuel and hydrocarbon raw materials. The air introduced into the area of the first reaction zone is the air added with oxygen through the air duct, and the position of the hydrocarbon feedstock is maintained at a high temperature environment above 1 900 ° C ... i (Comparative Example 1 7 ~ 2 1 ) Using the carbon black manufacturing furnace used in the examples, adjust the temperature of the combustion gas, the reaction stop position, the amount of potassium addition, the gas flow rate in the choke tube, etc. at the hydrocarbon feedstock introduction position to produce a comparison as shown in Table 1-9 Example 1 Carbon black with physical properties 7 to 18. In addition, Comparative Examples 19 to 21 are physical properties of commercially available carbon black. When each example is compared with Comparative Example 17, the Example has a higher PVC blackness than Comparative Example 17. This is because the particle diameter of Comparative Example 17 is outside the range prescribed by the third invention of the present invention. In addition, when each Example is compared with Comparative Example 18, the Examples have a higher T% 値. This point should be that the proportion of unaccompanied polycyclic aromatic hydrocarbons in carbon black is low, which means that carbon black is safer. The ratio N2SA / S EM of Comparative Example 18 is outside the range specified in the third invention of the present invention, and it also shows that the ratio of N2S A / S E ^ M and the ratio of unreacted polycyclic aromatic hydrocarbons are correlated. When each Example is compared with Comparative Example 19, Comparative Example 19 has a shorter heat aging time than the Examples. This should be the reason why P Η 値 is outside the range prescribed by the third invention of the present invention. When comparing the examples in each chapter with Comparative Examples 2 0 and 21, the paper size of Comparative Example 20 and ^ applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-"9- ^ Order Aw. (Please read the back first Please pay attention to this page and fill in this page again) 536551 B7 V. Description of the invention (117) 2 1 The dispersion index is larger than the embodiment, so the dispersion is not good. This point should be that cDBP is outside the scope of the third invention of the present invention. Table 1 9 Particle size N2SA SEM N2SA D1 / 2 D m 0 d D1 / 2 / D 7 5 nm m2 / g m2 / g / SEM nm nm D m 0 d nm Example 23 12 320 218 1.47 17 29 0.586 37 Example 24 11 360 240 1.50 15 25 0.6 31 Example 25 10.1 520 278 1.87 15 32 0.47 39 Example 26 8.3 694 313 2.2 11 26 0.423 41 Comparative Example 1 7 17 193 170 1.13 35 68 0.515 82 Comparative Example 1 8 11 301 235 1.28 17 26 0.654 63 Comparative Example 1 9 13 550 262 2.1 25 45 0.556 64 Comparative Example 20 15 300 182 1.65 22 31 0.71 165 Comparative Example 2 1 13 350 214 1.64 21 31 0.677 211 (Please read the Please fill in this page again for attention) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (continued) Dvs / D η 0 d cDBP cc / 1OOg pH 値 T% PVC blackness dispersion index heat aging time hr Example 23 1.27 67 6.5 99 30 125 280 or more Example 24 1:24 68 '6.8 99 32 130 280 or more Example 25 1.22 110 5.9 98 28 55 280 or more Example 26 1.58 110 6.2 99 33 85 280 or more Comparative Example 17 1.21 99 6.6 97 8 15 280 or more Comparative Example 1 8 2.42 70 7.1 65 30 260 280 or more Comparative Example 1 9 1.42 97 2.0 99 27 55 144 Comparative Example 20 5.32 44 6.5 98 29 720-Comparative Example 2 1 6.81 49 6.0 99 29 430-This paper size applies to China National Standard (CNS) A4 (210X297 cm) -120-536551 A7 B7 V. Description of the invention ( 118) (Examples 27 to 32) (Please read the precautions on the back before filling this page) Use the manufacturing furnace described above to trim the temperature of the combustion gas and the oxygen concentration of the combustion gas at the position where the hydrocarbon raw material is introduced ... The amount of raw materials supplied and the like are used to produce carbon black having physical properties as shown in Table 1-10. The fuel and hydrocarbon raw materials are phenolic oil. The air introduced into the area of the first reaction zone is introduced through an air duct with oxygen-added air, and the hydrocarbon material introduction position is maintained at a high temperature environment of more than 1 900 ° C. (Comparative Example 2 2 to 2 5) Using the carbon black manufacturing furnaces used in Examples 2 7 to 32, the temperature of the combustion gas, the reaction stop position, the amount of potassium addition, and the gas in the choke tube were adjusted at the hydrocarbon raw material introduction position. The flow rate and the like were used to produce a carbon black having physical properties of Comparative Example 22 shown in Table 1-10. In addition, Comparative Examples 2 3 to 2 5 are physical properties of commercially available carbon black. When each embodiment is compared with Comparative Example 1, the embodiment has a comparative example. It is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 2 2 Higher PVC blackness. This is because the N2SA of Comparative Example 1 is outside the range prescribed by the fourth invention of the present invention. When each Example is compared with Comparative Example 23, Comparative Example 2 has a shorter heat aging time than the Examples. This is because p 为其 is outside the range specified by the fourth invention of the present invention. When each example is compared with Comparative Examples 24 and 25, the comparative example has a larger dispersion index than the examples, and therefore, the dispersion is not good. This point should be 0 i / 2 / Dmod outside the scope of the fourth invention. This paper size is applicable to China National Standard (CNS) A4 (210X297mm) -121 · 536551

7 7 AB V. Description of the invention (119) Printed form of employee cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs_ 1 0 Particle size nm N2SA m2 / g D1 / 2 nm D m 0 d nm D1 / 2 / D m 0 d D75 nm D7 &quot; D m 0 d Example 27 16 241 24 -Φ5 0.533 54-1.2 Example 28 14 293 26 49 0.531 59 1.2 Example 29 12 320 17 29 0.586 37 1.28 Example 30 11 360 15 25 0.6 31 1.24 Example 31 10.1 520 15 32 0.47 39 1.22 Example 32 8.3 694 11 26 0.423 41 1.58 Comparative example 22 17 193 35 68 0.515 82 1.21 Comparative example 23 13 550 25 45 0.556 64 1.42 Comparative example 24 15 300 22 31 0.71 165 5.32 Comparative example 25 13 350 21 31 0.677 211 6.81 (Please read the precautions on the back before filling out this page) Table 1 10 (continued) DBP cc / 100g pH 値 &gt; vc blackness dispersion index heat resistance aging time hr Example 27 109 7.7 20 100 280 or more Example 28 132 5.8 13 10 280 or more Example 29 87 6.5 30 125 280 or more Example 30 96 6.8 32 130 280 or more Example 3 1 215 5.9 28 55 280 or more Example 32 157 6.2 33 85 280 or more Comparative example 22 122 6.6 8 15 280 or more Comparative example 23 150 2.0 27 55 144 Comparative Example 24 54 6.5 29 720 • Comparative Example 25 65 6.0 29 430-il. • 钃 丨 This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -122-536551 A7 B7_ V. Description of the invention (120) (Examples 3, 3, 4) (Please read the precautions on the back before filling out this page) Use the manufacturing furnaces of Examples 1 5 to 18 to adjust the combustion gas at the position where the hydrocarbon raw materials are introduced. The temperature, the oxygen concentration of the combustion gas, the supply amount of the i-material, etc. are used to produce carbon blacks with physical properties as shown in Table-11. Phenol and hydrocarbon raw materials are dyed phenol oil. The air introduced into the area of the first reaction zone is the air added with oxygen through the air duct, and the hydrocarbon feed material introduction position is maintained at a high temperature environment of more than 190 t. (Comparative Example 2 · 6 ~ 2 9) Using the carbon black manufacturing furnaces used in Examples 3, 3, and 4, the temperature of the combustion gas, the reaction stop position, the amount of potassium addition, and the inside of the choke tube were adjusted at the hydrocarbon material introduction position. The gas flow rate and the like were used to produce a carbon black having physical properties as shown in Table 11 and Comparative Example 26. In addition, Comparative Examples 2 7 to 2 9 are physical properties of commercially available carbon black. When each example is compared with the comparative example, the comparative example has a larger dispersion index than the example, so the dispersion is not good. The sheltering point should be the ratio of D B P / Dm0d, which is outside the scope of the present invention. Printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-123- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 &gt; &lt; 297 mm> 536551 A7 B7 V. Description of the invention (121) Table 1 1 Particle size nm N2SA m2 / g D1 / 2 nm D m 0 d nm D1 / 2 / D m 0 d D75-2 nm D75 / D m 0 d Example 3 3 10.1 520 15 -3-2 0.4 7 39-1.22 Implementation Example 34 8.3 694 11 26 0.423 41 1.58 Comparative example 26 16 241 24 45 0.533 54 1.2 Comparative example 27 12 320 17 29 0.586 37 1.28 Comparative example 28 15 300 22 31 0.71 165 5.32 Comparative example 29 13 350 21 31 0.677 211 6.81 ( Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Form 1 1 (continued) DBP cc / 100g DBP / D m 0 d pH 値 PVC Blackness Dispersion Index Heat Resistance Aging Time hr Example 33 215 6.72 5.9 28 55 280 or more Example 34 157 6.04 6.2 33 85 280 or more Comparative Example 2 6 109 2.42 7.7 20 100 280 or more Comparative Example 27 87 3.0 6.5 30 125 280 or more Comparative Example 2 8 54 1.74 6.5 29 720 • Comparative Example 29 65 2.1 6.0 29 430-(Example 3 5 to 3 9) The first reaction zone area with an inner diameter of 500 mm and an air diameter of 400 mm and an air introduction duct and a combustion chamber are sequentially connected, and a plurality of raw material nozzles are passed through the inner paper with a periphery connected to the first reaction zone area. Standards apply to China National Standards (CNS M4 (210X297)) -124- Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 536551 A7 B7 V. Description of the Invention (122). * Diameter 6 Omm, length 80 mm The second reaction zone area formed by the Ministry, and the third reaction zone area with an inner diameter of 100mm and a length of 600mm, and a control mechanism with a narrow mechanism. The inner valve diameter is 8mm. The structure of the carbon black manufacturing equipment. Among them, the entrance angle of the choke tube part is 90 °. Using the manufacturing equipment described above, the carbon black is manufactured under the conditions shown in Table-12. Among them, phenolic oil is used as the fuel and hydrocarbon raw materials. In Table 1, 12, “combustion gas temperature”, “combustion gas oxygen concentration” and “inside furnace pressure” are the values measured for the introduction of hydrocarbon raw materials. "Potassium concentration" refers to the concentration of K Ο Η added to the hydrocarbon feedstock, and is regulated in terms of potassium concentration. Various characteristics of the obtained carbon black are shown in Table-1 3. (Comparative Example 3 0 ~ 3 2) According to the carbon black manufacturing conditions shown in the examples, except that the flow velocity of the choke tube portion was changed to 2 7 m / s and 2 5 Om / s or less, the rest are based on the table-1 2 The physical properties of Carbon Black 'Comparative Example 30 manufactured under the conditions shown are shown in Table 1-13. Also Comparative Example 31 and Comparative Example 3 2 are physical properties of carbon blacks # 9 9 0 and # 9 6 0 sold by Mitsubishi Chemical Corporation. When the carbon black of the present invention is used for comparison with the comparative example, as shown in Table 1 13, when the examples are compared with the comparative example, Di / 2 / Dmod is smaller and the distribution of the aggregate diameter is more concentrated. In addition, it exhibits high blackness, and the dispersion index is also low, and the dispersion is good. (Please read the precautions on the back before filling this page) The size of the paper used for this edition applies to the Chinese National Standard (CNS) A4 (210X297 mm) · 125-536551 A7 B7 V. Description of the invention (123) (Example 40, Comparative Example 3 3) As described above, the implementation conditions and results of the simulation conditions of the carbon black using a computer are described in Example 40 of Tables 12 and 13; i Comparative Example 33. … A Comparison of Comparative Example 3 3 of Table 1 13 with Example 40 shows that it has a larger particle size, and this point should be because the choke tube inlet angle is outside the range of 45 to 100 degrees. (Please read the notes on the back before filling this page) The printed paper size of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standards (CNS) A4 specification (210X297 mm) · 126 · 536551 A7 B7 V. Invention Explanation (124) Table 1 12 Fuel air combustion gas Combustion gas Combustion gas raw material supply kg / h js. Temperature of the inner body oxygen concentration of choke tube kg / Nm2 / h degree t: dry-vo-1% flow rate m / sh-Example 3 5 53 530 1622 0.65 356 100 Example 36 52 500 1785 0.04 368 65 Example 37 54 530 1748 0.46 383 80 Example 38 54 520 1821 0.06 390 55 Example 39 52 500 1820 0.04 378 53 Comparative example 3 0 30 300 1620 0.65 207 45 Example 40 83 807 2000 0 459 110.9 Comparative example 3 3 83 807 2000 0 459 110.9 ---------- (Please read the precautions on the back before filling in this Page) Ordered by the Central Bureau of Standards of the Ministry of Economic Affairs, Consumer Consumption Cooperatives Table 1 12 (^ read) Pressure in the furnace kg / cm2G Potassium concentration ppm Inlet angle of choke tube ° _. Example 35 0.60 0 90 Example 36 0.58 0 90 Example 37 0.58 495 90 Example 38 0.54 0 90 Example 39 0.57 800 90 Comparative Example 3 0 0.2 500 90 Example 40 0.5 0 90 Comparative Example 3 3 0.5 0 15 One paper size applies the Chinese Standard (CNS) A4 (210X297 cm) -127-536551

7 7 AB V. Description of the invention (125) Table 1 1 Particle size nm N2SA m2 / g CrDBP cc / 100g D m 0 d nm D1 / 2 / nm -.--- ** D1 / 2 / ID m 0 d PVC Blackness Dispersion Index Example 35 24 120 90 70 33 0.471 5.3 10 Example 36 17 193 99 68 35 0.515 8.0 15 Example 37 20 163 74 40 23 0.575 12.3 40 Example 3 8 15 262 103 43 24 0.558 16.3 20 Example 39 '15 248 64 32 19 0.594 19.3 120 Comparative Example 30 22 156 75 54 60 1.11 6.7 60 Comparative Example 3 1 15 240 82 44 37 0.841 16.7 40 Comparative Example 32 15 240 60 44 37 0.841 18.3 180 Example 40 45 • • Comparative Example 3 3 27 _ • • • (Please read the notes on the back before filling out this page) (Example 4 1, 4 2) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs as shown in Figure-7槪 Sketch, a first reaction zone area with an air introduction duct and an internal diameter of 500 mm and a combustion chamber length of 1,400 mm is provided, and the first reaction zone area is connected to the first reaction zone area and has a plurality of raw material nozzles with an inner diameter passing through 50mm, 80mm length 2nd reaction zone area of choke tube section, and inner diameter 2 with quenching device 0 mm, 600 mm long Carbon black manufacturing furnace in the third reaction zone area. The position of the raw material nozzle is 100 mm from the entrance of the choke tube. The material of the choke tube is a double tubular structure made of deoxycopper phosphate. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm). · 128-536551 A7 _—_ B7 _ _ V. Description of the invention (126) The cooling device. The equivalent sand particle thickness ε of this material is 0. 4 5 mm. Using the above manufacturing furnace, carbon fish was manufactured under the conditions shown in Table-14. The fuel system uses propane gas, and the hydrocarbon raw material system uses phenolic oil (referred to as "feed oil" in Table-1-14). In Table 14, "in-furnace temperature", "oxygen concentration of combustion gas", and "flow velocity of combustion gas" are measured by the hydrocarbon raw material introduction site. "Oxygen concentration in combustion air" means the oxygen concentration in the air introduced by the air introduction duct. "Potassium concentration" refers to the concentration of KOH added to the hydrocarbon feedstock, and is regulated in terms of potassium concentration. Various characteristics of the obtained carbon black are shown in Table-15. (Comparative Example 3 4) Except that the inner diameter of the choke tube portion is 6 Omm, and the material of the choke tube portion is a high-purity alumina sheet, and the choke tube portion does not have a double structure, the rest are in accordance with Example 4 1 to 4 2 The contents set the same manufacturing device. The equivalent sand particle thickness ε of the alumina brick was about 3 mm. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (Comparative Example 3 5) The inner diameter of the choke tube section is 250 mm, and the material of the choke tube section is stainless steel Except for the cooling device having a double tubular structure, the same manufacturing device is provided according to the contents of Examples 41 to 42. (The equivalent sand grain thickness ε of the inner surface of the double tube made of stainless steel is 0.45 mm °) When the carbon black of the present invention is compared with the comparative example, 'as shown in Table 1 15, the paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) -129-536551 A7 B7 V. Description of the invention (127) · As a rule, when comparing the carbon black obtained in the example with the carbon black of the comparative example, Di / 2 / Dm〇d Smaller and more concentrated distribution of aggregate diameter. In addition, D 7 5 is also smaller, and there are fewer substances with large aggregate diameter. In addition, it exhibits a high degree of blackness, has a low dispersion index, and has a good dispersion. …… · — (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -130- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 536551

7 7 AB V. Description of the invention (128) Table 1 14 Example 41 Example 42 Comparative example 34 Comparative example 35 Fuel supply amount Nm3 / H 21.9 --- 2 5.6 21.8 -21.9 Combustion air amount Nm3 / H .450 450 520 450 Oxygen concentration% of combustion air 24.9 24.9 21.0 24.9 Oxygen concentration% of combustion gas 0.5 0.5 0.06 0.5 Flow velocity of combustion gas m / s 452 483 390 452 Raw material supply_Kg / H 36.5 75.2 55 36.5 Furnace temperature ° C 1857 1958 1821 1860 Potassium concentration ppm 0 765 0 0 Retention time of the choke tube section ms 2.21 2.07 2.05 0.69 (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy Table 1 1 5 Example 4 1 Example 42 Comparative Example 34 Comparative Example 35 Particle diameter nm 15 15 15 15 N2SA m2 / g 325 229 262 334 CrDBP cc / 100g 103 63 103 101 D m 0 d π m 42 41 43 52 D1 / 2 nm 20 19 24 45 D75 nm 48 52 53 101 Dvs / Dmod index 1.14 1.27 1.23 1.94 PV.C Blackness index 21.0 25.0 16.3 19.3 Dispersion index 10 40 20 50 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 131-536551 A7 B7 V. Hair Explanation (129) (Example 4 3 to 4 7) As shown in the schematic diagram of FIG. 7A, a first reaction zone region having an inner diameter of 500 mm and an inner diameter of 500 mm and a length of 1400 mm in order is provided, and the first reaction zone area corresponding to the first The reaction zone area is connected to a second reaction zone area with an inner diameter of 60 mm and a length of 800 mm and a plurality of raw material nozzles, and an inner diameter of 100 mm with a quenching device. A carbon black manufacturing furnace composed of a 3,600 mm long third reaction zone region and a control valve with a narrow mechanism with an internal flap diameter of 80 mm. Using the above manufacturing apparatus, carbon black was manufactured under the conditions shown in Table 1-16. Fuel and hydrocarbon raw materials are dyed phenol oil. In Table 16, "temperature of combustion gas", "oxygen concentration of combustion gas", and "pressure in the furnace" are the values of krypton measured at the place where the hydrocarbon raw material is introduced. "Potassium concentration" refers to the concentration of K Η 添加 added to the hydrocarbon feedstock, and is regulated in terms of potassium concentration. Various characteristics of the obtained carbon black are shown in Table-17. (Comparative Example 3 6 to 3 9) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The length of the choke tube section of the carbon black manufacturing furnace used in the example was changed to 500 mm. According to Table 1, 16 The carbon blacks of Comparative Examples 3 to 3 to 7 were produced under the conditions shown in Table 1-17. Also Comparative Example 38 and Comparative Example 39 are physical properties of carbon blacks # 9 9 0 and # 9 6 0 sold by Mitsubishi Chemical Corporation. When the obtained carbon black of the present invention is compared with the comparative example, as shown in Table 1, when the example is compared with the comparative example, Di / 2 / Dmod is small and the aggregate is 132. (Please read the precautions on the back first (Fill in this page again.) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7. 5. Description of the invention (13) The diameter distribution is more concentrated. In addition, D75 is also smaller, and there are fewer substances with large aggregate diameter. In addition, it exhibits a high degree of blackness, a low dispersion index, and a good degree of dispersion. (Example 4 8 and Comparative Example 40) As mentioned above, the implementation conditions and results of the simulation conditions of carbon black using a computer are described in Example 48 and Comparative Examples in Tables 16 and 17 4 in 0. Comparison of Comparative Example 40 of Table 17 with Example 4 8 shows that it has a larger particle size, and this point should be because the choke tube inlet angle is outside the range of 45 to 100 degrees. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs-133 · This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 536551 A7 B7 V. Description of the invention (131) Table 1 16 Fuel air combustion gas Combustion gas Combustion gas raw material supply kg / h Volume of the oxygen concentration of the volume of choke pipe kg / Nm2 / h Duyi dry-vO-l ·% Flow rate m / sh -Example 43 53 530 1622 0.65 356 100 Example 44 52 500 1785 0.04 368 65 Example 45 54 530 1748 0.46 383 80 Example 46 54 520 1821 0.06 390 55 Example 47 52 500 1820 0.04 378 53 Comparative Example 3 6 52 520 1625 0.65 353 85 Comparative Example 3 7 52 500 1770 0.04 369 70 Example 4 8 83 807 2000 0 459 110.9 Comparative Example 4 0 83 807 2000 0 459 110.9 (Please read the precautions on the back before filling this page) Economy Printed by the Central Bureau of Standards Consumer Cooperatives Table 1 16 (continued) Pressure in the furnace kg / cm2G Potassium concentration ppm Convection time in the narrow part ms Length of choke tube mm Entry angle of choke tube ° Example 43 0.60 0 2.2 5 800 90 Example 44 0.58 0 2.17 800 90 Example 45 0.58 495 2.09 800 90 Example 46 0.54 0 2.05 800 90 Example 47 0.57 800 2.11 800 90 Comparative Example 36 0.45 80 1.42 500 90 Comparative Example 3 7 0.42 0 1.35 500 90 Example 48 0.5 0 2.4 1000 90 Comparative Example 4 0 0.5 0 2.4 1000 15 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -134-536551 B7 V. Description of the invention (132) Table 1 1 7 Particle size nm N2SA m2 / g CrDBP cc / 100g ID m 0 d nm Dl / 2 nm D1 / 2 / D m 0 d-:: D75 nm Example 43 24 120 90 70 33 0.471 86 Example 44 17 193 99 35 0.515-'82 Example 45 20 163 74 40 23 0.575 49 Example 46 15 262 103 43 24 0.558 53 Example 47 15 248 64 32 19 0.594 41 Comparative Example 36 23 130 96 68 42 0.618 124 Comparative Example 37 19 175 85 57 35 0.614 93 Comparative Example 38 15 240 82 44 37 0.841 67 Comparative Example 39 15 240 60 44 37 0.841 75 Example 48 45 Plug • • _ • • Comparative Example 40 27------(Please (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 1 7 (continued) D75 / Dmod PVC Blackness Dispersion Index Example 43 1.23 5.3 10 Example 44 1.20 8.0 15 Example 45 1.23 12.3 40 Example 46 1.23 16.3 20 Example 47 1.28 19.3 120 Comparative Example 3 6 1.82 6.3 20 Comparative Example 3 7 1.63 8.0 30 Comparative Example 3 8 1.52 16.7 40 Comparative Example 3 9 1.70 18.3 180 Example 4 8-• Click on Comparative Example 4 0---This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 Mm) -135-536551

7 7 A B V. Description of the invention (133). (Examples 49 to 5 1) Using the manufacturing furnaces of Examples 1 to 4, carbon black was produced under the conditions shown in Table 1-18. The combustion chamber uses the device shown in Figure-4. The fuel and carbonized gas raw materials are dyed phenol oil. Example 5 In 0, --forbearance-. 1, oxygen may be added to the air in order to increase the burning-burning temperature. Various characteristics of the obtained carbon black are shown in Table 1-19. (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau, Ministry of Economic Affairs, Table 1 1 Example 49 Example 50 Example 5 1 Particle diameter nm 15 12 11 N2SA m2 / g 262 320 360 cDBP cc / 100g 103 67 68 D m 0 d Π HI 43 29 25 D1 / 2 nm 24 17 15 D75 nm 53 37 31 PVC blackness index 16.3 30.0 32.0 dispersion index 20 125 130 Table 1 1 8 Example 49 Example 50 Comparative Example 5 1 Fuel kg / h 54 54 58 Air volume Nm3 / h 520 470 (13) 480 (20) Combustion gas temperature ° C 1821 1920 2090 Oxygen concentration% of combustion gas 0.06 0.39 0.58 Cooling water volume m3 / h 3 5 5 Detection temperature t 286 298 305 Combustion chamber appearance flaws 4 \\\ No damage is good No damage is good No damage is good () 値 is the oxygen flow rate This paper applies Chinese national standard (CNS) A4 specification (210X297 mm) ) -136 _ 536551 A7 _B7___ V. Description of the invention (134). It is learned that high temperature combustion gas can be obtained without causing the front end part of the combustion chamber to be melted, and high temperature combustion gas with the smallest heat release from the combustion chamber can be obtained. Moreover, the gas exchange is easy in the atomization part when the temperature is raised, and the exchange is completed in a short time, so the rattan surface of the combustion part will not be impacted by the rapid cooling, and the damage of the brick surface can be prevented. (Examples 52 to 54) A first reaction zone region having an inner diameter of 500 mm and an inner diameter of 500 mm and a length of 1,400 mm as shown in the outline of FIG. 8 is shown in sequence, and the first reaction zone is provided. The second reaction zone area with an inner diameter of 60 mm and a length of 800 mm is provided by a plurality of raw material nozzles through the peripheral connection, and an inner diameter of 100 mm with a quenching device and a length of 60 A carbon black manufacturing furnace composed of a 0 mm 3rd reaction zone area and a control valve having a narrow mechanism with an internal flap diameter of 80 mm. Using the above manufacturing apparatus, carbon black was manufactured under the conditions shown in Table = 20. Fuel and hydrocarbon raw materials are dyed phenol oil. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). In Table 1, "temperature of combustion gas", "oxygen concentration of combustion gas" and "pressure inside the furnace" are値 measured at the site where the hydrocarbon feedstock was introduced. "The gas flow in the second reaction zone area @" means the volume of combustion gas divided by the cross-sectional area of the furnace containing hydrocarbon feedstock. The "insertion length of the hydrocarbon feed nozzle" refers to the distance between the front end of the hydrocarbon feed nozzle and the wall surface. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -137- &quot; ~ Printed by the Shelling Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 536551 A7 B7__ 5. Description of the invention (135) "Cross-cut area in the furnace "Reduction rate" refers to the area obtained by removing the area of the hydrocarbon feed nozzle divided by the area of the cross section of the furnace containing the area of the hydrocarbon feed nozzle. • A "nozzle flow rate" refers to the flow of combustion gas at the insertion-position of the hydrocarbon-raw-material introduction nozzle, divided by the cross-sectional area of the second reaction zone area minus the area occupied by the hydrocarbon raw material nozzle. The gas flow rate obtained by cutting the area. Various characteristics of the obtained carbon black are shown in Table-2. (Example 5 · 5) As shown in FIG. 10, a first reaction zone region having an inner diameter of 100 mm and a length of 500 mm was simulated on a computer, and the first reaction zone region was connected to the first reaction zone region and had a protrusion. Raw material oil with a length of 20 mm and a length of 50 mm is introduced into the second projection zone of the nozzle projection with an inner diameter of 60 mm and a length of 800 mm, and a carbon formed by a third reaction zone with an inner diameter of 100 mm and a length of 700 mm. Black manufacturing furnace. The internal settings of this model are physical properties with a density of 0 · 184 kg / m3, a viscosity of 6-· 52E-5 kg / ms, and the flow velocity of the inlet of the combustion gas is 3 5 · 2 m / s, and the pressure loss is calculated. The turbulence model uses a standard k-ε model. (Comparative Example 4 1) As shown in FIG. 11, a first reaction zone region having an inner diameter of 100 mm and a length of 500 mm was simulated on a computer, and connected to the first reaction zone region, and had a resistance The second reaction zone area of the inner diameter of the trachea part is 20mm, and the length is 800mm, and the inner diameter is 100mm, and the length is 700. This paper size applies the Chinese National Standard (CNS) A4 specification (210 &gt; &lt; 297 (138mm) 138- &quot; (Please read the notes on the back before filling this page) Order 536551 A7 _____B7___ V. Description of the invention (136) mm Carbon black manufacturing furnace composed of the 3rd reaction zone. And calculate the pressure loss when the inlet velocity is 35 · 2m / s. The physical properties of the gas, the turbulent flow model, and the like are the same as those in the embodiment 5-5. ~ The calculation conditions are the pressure loss conditions as shown in Table 1-20. In addition, the pressure loss is the difference between the maximum 値 and the minimum 静 of the static pressure in the furnace. When comparing Example 5 5 with Comparative Example 41, the pressure loss in the furnace is smaller than that in Example 5 and part 5 in the example. Because the pressure loss at the introduction position of the hydrocarbon raw material is small, the flow velocity of the combustion gas can be reduced by High speed flow near Mach 1. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) -139-536551

7 7 AB Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (137) Table 1 2 Example 52 Example 53 Example 54 Example 55 Comparative Example 41 Fuel kg / h 53 5 2 --- 52 Amount of mold air Nm3 / h 530 500 500 which • Temperature of combustion gas ° C 1622 1785 1820 1800 1800 Oxygen concentration of combustion gas vol% 0.65 0.04 0.04--2nd reaction zone inner diameter mm 60 60 60 60 20 2 Gas flow velocity in the reaction zone area m / s 356 368 378 97.7 880 Insertion length of hydrocarbon raw material introduction nozzle mm 20 20 20 20 0 Reduction rate of cross-sectional area in the furnace% 58.7 58.7 58.7 88.9 0 Nozzle flow velocity m / s 862 891 915 880 880 Nozzle flow rate Mach 0.99 0.98 0.99 0.96 0.96 Feed oil introduction kg / H 100 65 53 Pressure in the furnace kgf / cm2G 0.60 0.58 0.57 0.5 0.5 Pressure loss in the furnace kgf / cm2-1.3 1.8 (Please read the precautions on the back first (Fill in this page again.) This paper size is in accordance with Chinese Standard (CNS) A4 (210X297mm) 140 · 536551 A7 B7 V. Description of the invention (138) Table 1 2 1 Example 52 Example 53 Example 54 Particle size nm 24 1 7 15 N2SA m2 / g 120 19-3-248 cDBP cc / 1 OOg 90 99 64 D m 0 dnm 70 68 32 D1 / 2 nm 33 35 19 D 1/2 / ID m 0 d 0.471 0.515 0.281 PVC blackness index 5.3 8.0 19.3 Dispersion index index 10 15 120 (Please read «Notes on the back side before filling out this page） Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. In the following description, the chemical composition% of refractory refers to the weight % 〇 (Example 5 6) (1) The shape of the furnace is sequentially provided with a combustion chamber having an internal diameter of 500 mm and a length of 1400 mm, which can cause a mixture of air containing sufficient oxygen and LPG fuel to combust and generate a high temperature combustion air stream of 2 2 0 t. The first reaction zone region and two nozzle ducts connected to the first reaction zone region and penetrating the phenolic oil as the raw material oil into the high-temperature combustion gas flow have an inner diameter of 50 mm and a length of 300 mm. The second reaction zone area of the choke tube section and the inner diameter of the third reaction zone area, which is 100mm in length and 6000mm in length, can be stopped by cooling water spraying. (CNS) A4 size (210X297 mm) .141 -Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 536551 A7 B7 V. Description of Invention (139) · Furnace-type carbon black manufacturing furnace. (2) Refractory materials constituting the furnace • Less than the previous furnace, the refractory materials used up to the introduction zone of the raw material oil in the first reaction zone-and the second reaction zone-zone are from the inside Magnesium oxide mold material (chemical composition: MgO 9 9¾), mold construction layer, bonded magnesia-chrome brick (chemical composition: MgO 66 ° / 〇, Cr203, 20%, Fe203, 7%), high alumina It consists of four-layer structure such as high-quality bricks and refractory boards; the second reaction zone area is made of high-alumina refractory material from the inside after the refractory material is introduced from the raw material oil (A 1 2 0 3 99%, Si〇2 0.2¾, Fe 2 0 3 2), alumina-based ingot, refractory plate and other three-layer structure; the third reaction zone area from the inner surface is the aforementioned high-alumina brick, alumina-based ingot and other two layers Constructed by. (3) The shape and properties of the mold before and after the actual operation are based on the surface temperature of the furnace at 180 ° C. After 2 months of continuous operation, the temperature of the mold is checked and the condition in the furnace is not found. Shedding phenomenon. When measuring the change in the thickness of the mold material layer after two months of operation, it was found that after two months of operation at a furnace surface temperature of 180 ° C, the thickness also decreased by only about 2 mm. In addition, the composition of the surface of the mold material before and after the operation is as shown in Table-2, there is no significant change before and after the operation, but it becomes the paper standard applicable to Chinese national standards (CNS> A4 specification (210X297 mm)). 142-(Please read the precautions on the back before filling in this page) Order 536551 A7B7 V. Description of the invention (140). It can improve the composition of the fire resistance. Also, the porosity may not change, so the fire resistance does not decrease. It can be seen that, even under the actual operation of ultra-high temperature, the carbon black manufacturing furnace obtained by processing the mold material is a very practical manufacturing furnace. F.-Table 1 2 After the new product is used (2 months) Remarks Mg 〇 9 9 • 4 9 丨 9 • 8 Fe2〇3 0 · 1 0 .1 AI2O3 0 · 1 &lt; 0 • 01 Si〇2 0 · 1 &lt; 0 • 01 Decrease: Fire resistance Ti〇2 0. 1 0 1. 0 6 Increase C Γ 2 〇3 &lt; 0 · 0 1 &lt; 0 • 01 Ca〇 &lt; 0 · 0 1 &lt; 0 • 01 count 10 0 .0% I 〇 丨 0 .0% Rate 30.0% 29.8% Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (Notes on this page, please fill in this page again) (Example 5 7) (1) The shape of the furnace is sequentially provided with a combustion chamber with a combustion chamber capable of mixing air containing sufficient oxygen and LPG fuel to generate a high-temperature combustion air stream at 1750 ° C. The first reaction zone area with an inner diameter of 500mm and a length of 1400mm is connected to the first reaction zone area, and there are two penetrating phenols that can be used as raw oil. The paper size is in accordance with Chinese National Standard (CNS) A4. (210X297 mm) -143-536551 A7 B7 V. Description of the invention (141) The second reaction zone area of the nozzle duct with the inner diameter of 5 Omm and the length of 300mm with the choke tube section of the oil introduction high-temperature combustion gas flow is provided in the Downstream of the second reaction zone, a cooling water spray method can be used to stop the inside diameter of 100mm and a length of 6000mm. · 3. A furnace-type carbon black manufacturing furnace constructed in the reaction zone. (2) The refractory constituting the furnace is In the former furnace, the refractory used in the entire first reaction zone and the raw material oil introduction position in the second reaction zone is a double-bonded magnesia-chrome brick (chemical composition: M g 0 6) 6%, C r 2 〇 a 20%, Fe203 7%) High alumina brick, refractory plate and other three-layer structure; the second reaction zone is made of high-alumina refractory from the inside after the refractory after the introduction of raw material oil (chemical composition A 1 2 0 3 9 9%, Si〇2 0.2%, Fe203 (0.2%)), alumina-based ingot, refractory plate and other three-layer structure; the third reaction zone area from the inside is Yu Shu's high-alumina bricks, alumina-based It consists of a two-layer structure such as an ingot. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs After the above-mentioned manufacturing furnace has been continuously operated for 50 hours, the comparison between the type of the innermost refractory, the characteristics of the produced carbon black, and the manufacturing conditions is shown in Table-2 3 As shown. (Embodiment 5 8) A set of the same shape as in Embodiment 5 7 is provided to have a mixture of LPG fuel and air with sufficient oxygen to produce 1 7 50 ° C high-temperature combustion. 144- (Please read the note on the back first) Please fill in this page again) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) 536551 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (142) Combustion chamber for gas flow. The refractory used was the same as in Examples 5 to 7. After 50 hours of continuous operation of the manufacturing furnace, the comparison between the type of the innermost refractory, the characteristics of the produced carbon black, and the manufacturing conditions ^ 1 倂 It is included in Table 1 2 3. First (Embodiment 5 9) A combustion chamber having the same shape as that of Embodiment 5 7 and having a mixture of air containing sufficient oxygen and LPG fuel to generate a high-temperature combustion air stream at 2000 ° C was provided. The refractory used was the same as in Example 1. After 50 hours of continuous operation of the manufacturing furnace, the comparison between the type of the innermost refractory, the characteristics of the produced carbon black, and the manufacturing conditions is included in Table 1 2 3 at a time. (Embodiment 60) A combustion chamber having the same shape as that of Embodiment 57 is provided, and has a combustion chamber in which a mixture of air containing sufficient oxygen and LPG fuel can be combusted to generate a high-temperature combustion air stream at 2000C. The refractory used in Example 5 was the refractory material used in the entire first reaction zone and the raw material oil introduction position in the second reaction zone in Example 5 and was changed to a double-bonded magnesium-chromium starting from the inner surface. Brick (chemical composition is M g0 〇 0 ％, C r 203 2 0%, Fe 2 0 a 4%), high alumina brick, refractory board and other three-layer structure. After 50 hours of continuous operation of the manufacturing furnace, the comparison between the type of the innermost refractory, the characteristics of the produced carbon black, and the manufacturing conditions is as follows (please read the precautions on the back before filling this page). This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) -145-536551 A7 B7__ 5. Description of the invention (143) is included in Table 1 23. (Embodiment 61) A combustion chamber having the same shape as that of Embodiment 57 is provided, which has a combustion chamber in which a mixture of air with sufficient oxygen and LPG fuel is mixed and combusted to generate a high-temperature combustion air stream at 2000C. The refractory used in the example 5 is the refractory material used in the entire first reaction zone and the raw material oil introduction position in the second reaction zone in Example 5 and was replaced with a directly bonded magnesium-chrome brick from the inner surface. (Chemical composition is MgO 70% * Cr 2 0 3 20%, F e 2 0 3 4%), high alumina brick, refractory board and other three-layer structure. After 50 hours of continuous operation of the manufacturing furnace, the comparison between the type of the innermost refractory, the characteristics of the produced carbon black, and the manufacturing conditions is included in Table 1 2 3 at a time. '' (Comparative Example 4 2) '' Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Set a shape with the same shape as in Example 5 and 7. Combustion chamber in which air is mixed with LPG fuel to produce a high-temperature combustion air stream at 1750 ° C. The refractory used in the example 5 is the refractory used in the entire first reaction zone and the raw material oil introduction position of the second reaction zone in Example 5 to a high alumina refractory starting from the inner surface ( It has a structure consisting of a two-layer structure such as a chemical composition A 1203 99%) and a refractory plate. After 50 hours of continuous operation of the above-mentioned manufacturing furnace, the innermost refractory of this paper is sized according to the Chinese National Standard (CNS) A4 (210X297 cm). 146-536551 A7 B7 V. Types of Invention Description (144) The content of comparison with the characteristics and manufacturing conditions of the carbon black obtained is included in Table 1-23. • 、 II- (Please read the precautions on the back before filling in this page) (Comparative Example 4 3) A- Let®1 have the same shape as in Example 5 7 and have a mixture of LPG fuel and air with sufficient oxygen Combustion chamber producing a high-temperature combustion air stream at 1 900 ° C. The refractory used is the same as that of Comparative Example 42. After the manufacturing furnace is continuously operated for 50 hours, the comparison between the type of the innermost refractory, the characteristics of the produced carbon black, and the manufacturing conditions is as follows: Included in Table 1 2 3. (Comparative Example 4 4) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. The same shape as in Example 5 and 7 has a shape that allows the air containing sufficient oxygen to be mixed and burned with LPG fuel to produce a high temperature combustion air stream at 1750 ° C Combustion chamber. The refractory used in Example 5 7 is the refractory used in the entire first reaction zone and the raw material oil introduction position in the second reaction zone. The chrome oxide refractory starting from the inner surface (chemical It consists of a three-layer structure consisting of ZrO2 99%), high alumina refractory, and refractory board. After 50 hours of continuous operation of the manufacturing furnace, the comparison between the type of the innermost refractory, the characteristics of the produced carbon black, and the manufacturing conditions is included in Table 1 2 3 at a time. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 cm). 147. 536551 A7 B7 _ V. Description of the invention (145) · (Comparative Example 4 5) Setting 1 has the same shape as Example 5 7 and has a Combustion chamber that can mix air with sufficient oxygen and LPG fuel to produce 1 900 ° C ii temperature combustion airflow. The refractory materials used are the same as those in Comparative Example 4 4- The comparison between the type of the innermost refractory and the characteristics of the produced carbon black and the manufacturing conditions after 50 hours of continuous operation of the manufacturing furnace described above Then one count is counted in Table One 23 (Table 1 23-1 to Table-23-3). ------ Order (please read the notes on the back before filling this page) The paper size printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies the Chinese national standard (CNS &gt; Α4 size (210 × 297 mm) -148 · 536551 A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (146) Table 1 2 3 1 Example 5 7 Example 5 8 Example 5 9 Magnesia-chrome brick refractory used on the innermost surface Magnesia-chrome brick refractories Magnesia-chrome brick refractory (double-bond) (double-bond) (double-bond-) Main ingredients (%) Mg〇66 MgO 66 MgO 66 Cn〇3 20 Cr2〇3 20 Cn〇 3 20 Fe2〇3 7 F e 2〇2 7 Fe2〇2 7 Temperature of high temperature gas 1750 1900 2000 ° · rc) 15 12 10 of carbon black produced Particle size (nm) _2 Amount of LPG for fuel 10 12 14 ( Nm3 / h) Combustion air volume 350 350 350 (Nm3 / h) Oxygen concentration (%) 21 25 27__ Carbon content of a lifetime 12 16 11 (kg / h) Good transportation for 50 consecutive days (no turtle good (No turtle is good (no ^ cracked or dissolved refractory after turning) Cracked or dissolved) Cracked or dissolved) Condition (please first Read the notes on the reverse side and fill in this page) This paper size is applicable to Chinese Standard (CNS) A4 (210X297 mm) -149- 536551 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ) Table 1 2 3 2 Example 6 0 Example 6 1 Comparative Example 4 2 Magnesia-chrome brick refractory for palladium on the innermost surface Mg-chrome brick refractory High alumina refractory (semi-double-bonded) (direct Tinder-Main ingredients (%) Mg〇70 Mg〇75 Al2〇399 Cr2〇3 20 Cr2〇3 10 Fe 2 0 3 4 Fe2 0 2 4 High temperature gas temperature 2000 2000 1750 degrees WrC) 10 of carbon black produced 10 15 Particle size (nm) * 2 Amount of LPG for fuel 14 14 10 (Nm3 / h) Amount of air for combustion 350 350 350 (Nm3 / h) Oxygen concentration (%) 27 27 21 Amount of carbon produced 11 11 12 ( kg / h) Good transportation for 50 consecutive days (no turtle is good (there is no crack or dissolution of the refractory material after the edge of the turtle has turned slightly) crack or dissolution) abrasion status (please read the precautions on the back before filling (This page) P. The size of the paper used for this edition applies to the Chinese National Standard (CNS) A4 specifications ( 210X297 male). 150- 536551

A B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (148) Table 1 2 3 3 Comparative Example 4 3 Comparative Example 4 4 Comparative Example 4 5 The innermost refractory oxyaluminous refractory oxidation Chromium refractory Chromium oxide refractory main component (%) Al2〇399 Zr〇295 ZrO: 95 temperature of high temperature gas Wfc) 1900 1750 1900 particle size of carbon black (nm) * 2 12 15 12 LPG amount for fuel ( Nm3 / h) 12 10 12 Amount of air for combustion (Nm3 / h) 350 350 350 Oxygen concentration (%) 25 21 25 Carbon produced (kg / h) 16 12 16 Refractory condition after 50 days of continuous operation The larger dissolution part has fine cracks, cracks and part of it (please read the precautions on the back before filling this page) * 1: The measurement of the high temperature gas temperature in the furnace is measured with a radiation thermometer. 2: The particle size of the produced carbon black is measured using an electron microscope method. The electron microscope method is the method described below. Put carbon black into chloroform and irradiate it with 2 0 OKHz ultrasonic waves for 20 minutes to disperse it. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -151-536551 A7 _ · _B7_ V. Description of the invention (149) After 'fix the dispersed sample with a support membrane. Photograph it with a transparent electron microscope, and calculate the grain size based on the diameter of the photo and the magnification of the photo (please read the precautions on the back before filling in this page). This operation was carried out about 1 500 times, and the arithmetic mean was used to determine 値. 1 In the following Examples 6 2 to 6 4 and Comparative Examples 4 6 to 5 3, phenol oil was used as the hydrocarbon raw material (raw oil). In addition, the estimated gas temperature is based on the heat transfer calculation measured by the thermoelectric pair embedded in the furnace wall, and is based on the formula:

Q = AAAT / L (This formula is called the Fourier formula, where Q is the heat transfer per unit time 'λ is the thermal conductivity, A is the area through which heat passes, ΔΤ is the temperature difference between 2 points, and L is 2 The distance between points) is used as a reference to calculate the heat transfer, and the measured temperature is calculated by computer simulation using the element limitation method in consideration of the shape of the furnace. ——Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (Example 6 2) As shown in FIG. 12, an inner wall is provided with magnesium oxide chromium oxide bricks of 70% by weight and 18% by weight of chromium oxide. The maximum pipe diameter is 400mm, the length is 2000mm, the convex angle of the narrow part is 15 °, and the final exit diameter is 60mm in the first zone area (combustion area), and the first reaction zone area is connected to the first reaction zone area by an internal diameter of 60mm and a length of 1. 0 0 Omm The second zone area formed by the choke tube section (reaction zone area-152 · This paper size applies Chinese National Standard (CNS) A4 standard (21〇 &gt; &lt; 297 mm) 536551 A7 B7 V. Description of the invention (150)), and a furnace-type carbon black manufacturing furnace constituted by a third zone region with an inner diameter of 200 mm and an axial length of 300 mm connected to the second reaction zone region, which can be introduced with cooling water to stop the reaction And use it to make carbon black. The front part of the choke tube in this manufacturing device includes the introduction of raw oil. The vertical system is a metal (copper) inner diameter of 60 mm, which can be cooled by forced water cooling, and the axial length is 200 mm. It is set at a position of 100mm from the choke tube inlet section. Secondly, the inner diameter of the rear section of the choke tube section is the same as the front section of 60mm, the axial length is 800 mm, and the content of sand dioxide is less than 0.5wt%. Alumina inner wall. The third zone is composed of alumina bricks which are the same as those in the rear part of the narrow portion. In the figure, 1 is the first reaction zone area, 2 is the second reaction zone area, 2 a is the front part of the choke tube, 2 b is the rear part of the choke tube, and 3 is the third reaction zone area. Carbon black is manufactured by setting the temperature of the gas at the entrance of the second zone to 2000 ° C, and adding potassium to the hydrocarbon raw material. The manufacturing conditions and the contents of the obtained carbon black monster are shown in Table-2. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Example 6 3) Using the device shown in Figure 12 to set the temperature of the gas at the entrance of the second zone to 2000 ° C, the potassium concentration in the hydrocarbon feedstock is 1,000. Carbon black is produced under the conditions of PP m. The manufacturing conditions and the physical properties of the carbon black produced are shown in Table 1 2 4. (Example 6 4) • 153- (Please read the notes on the back of -M before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 __ · _B7__ V. Description of the invention (151). Using the apparatus shown in Figure 12, carbon black was produced under the conditions that the gas temperature at the entrance of the second zone was set to 2000 ° C and the potassium concentration in the hydrocarbon feedstock was 4,000 ppm. The manufacturing conditions and the content of the obtained carbon black are shown in Table 1 2 4. … Table 1 2 4 Example 62 Example 63 Example 64 Fuel air supply Nm3 / h 500 500 500 Same oxygen concentration VOL.% 26.0 26.0 26.0 Fuel supply kg / h 63.0 63.0 63.0 Band 2 area Oxygen at the inlet ° C 2000 2000 2000 Temperature Flow velocity at the inlet of the second zone m / s 426 426 426 Feed oil supply kg / h 140.0 140.0 140.0 Potassium concentration in raw oil ppm 0 1000 400 Deformation of the second zone In the case of 2 1 mm to 1 mm to 1 mm, the particle size is 2 nm 22.3 22.2 22.0 DBP oil absorption mL / 1 OOg 153 81 102 ash% 0.03 0.23 0.11 D m 〇d nm 95 76 84 D 7 5 nm 119 98 106 Printed by Shelley Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) M specification (210X297 mm) -154-536551 A7 B7 _ V. Description of the invention (152) (Comparative Example 4 6) Except for using the manufacturing apparatus shown in the schematic diagram in Figure 13 and Figure 3, carbon black was manufactured under the same conditions as in Example 62. In this manufacturing device, the "gas choke tube part is made of alumina bricks with a silica content of 0.5%-below" and has an inner diameter of 60 mm and a length of 1,000 mm in the axial direction, of which The hydrocarbon raw material introduction device is set at a position of 100 mm from the entrance of the choke tube. It was implemented under the condition that the potassium concentration in the hydrocarbon feedstock was 100 p ppm. The manufacturing conditions and the physical properties of the carbon black produced are shown in Table 1 25. It is known from the table that in order to obtain the same small particle size as in the example, the supply of raw oil must be reduced, which will cause Productivity has deteriorated. (Comparative Example 4 7) Use the manufacturing equipment shown in the schematic diagram in Figure 13 to increase the concentration of oxidizing gas and the fuel concentration, and set the gas temperature at the inlet of the second zone to 1950 ° C. Manufactured carbon black, and learned that the bricks of the choke tube section had been deformed after a while. The manufacturing conditions are shown in Table 1 25. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back before filling out this page) (Comparative Example 4 8) Use the manufacturing equipment shown in the schematic diagram in Figure 13 to increase the concentration of oxidizing gas And the fuel concentration, and the temperature of the gas at the entrance of the second zone was set to 2000 ° C, and the potassium concentration in the raw material oil was 1000 ppm. Carbon black was produced. It was found that the obstruction of the choke tube had been deformed after one day. The manufacturing conditions and the physical properties of the carbon black produced are shown in Table-2. It is learned that the second paper size is applicable to the Chinese National Standard (CNS) M specification (210X297 mm) 7l55- 536551 A7 _____B7_ V. Description of the invention ( 153). There is a damage of 2 Omm in the inner wall of the belt area, and carbon black with excellent quality cannot be continuously produced. Printed by the Consumers 'Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Table 1 2 Comparative Example 46 Comparative Example 47 Comparative Example 48 Fuel Air Supply Nm3 / h 500 500 500 Same Oxygen Concentration VOL.% 21.0 24.0 26.0 Fuel Supply' kg / h 51.0 58.0 63.0 Oxygen at the entrance of the second zone ° C 1800 1950 2000 Temperature Flow velocity at the entrance of the second zone m / s 385 415 426 Feed oil supply kg / h 90.0 120.0 120.0 Potassium concentration in feed oil ppm 1000 1000 1000 Deformation of the second zone area after 2 M. 20 mm after 1 month, the deformation damage diameter nm 22.2 22.0 DBP oil absorption mL / 1 OOg 81 80 ash% 0.24 0.22 D m 〇d nm 77 80 D 7 5 nm 102 146 (Comparative Example 4 9) (Please read the notes on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) _ 156 536551 A7 _____B7 V. Invention Explanation (154) As shown in the outline of FIG. 14 (b), the entire second zone area (tube inner diameter of 60 mm, length of 1,000 mm) containing a forced water cooling structure made of metal (copper) is used. Carbon black Manufacturing apparatus, and sets' § 2 with the inlet gas temperature region 2 0 0 0 ° C ..., ... potassium concentration in raw material oil - for the manufacture of carbon black under a condition of 0 P pm. The manufacturing conditions and physical properties of the carbon black produced are shown in Table-26. It is known that the oil absorption and aggregate diameter of D B P are large. (Comparative Example 50) Carbon black was produced in the same manner as in Comparative Example 49 except that the potassium concentration in the feedstock oil was set to 1000 p p m. The manufacturing conditions and the physical properties of the carbon black obtained are shown in Table 1 26. It is known that the oil absorption of D B P and the aggregate diameter (Dm.d) are large. (Comparative Example 5 1) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ----------- (Please read the precautions on the back before filling out this page)-Order-In addition to the concentration of potassium in raw oil Except for the setting of 8 0 0 0 p pm, carbon black was produced in the same manner as in Comparative Example 4 9. The manufacturing conditions and physical properties of the carbon black obtained are as shown in Table-2 '. It is known that the ash content is large. This paper size applies the Chinese National Standard (CNS) A4 (210X297 cm) -157- 536551 A7 B7 V. Description of the invention (155) Table 1 2 6 Comparative Examples Comparative Examples 49 50 51 Fuel air supply Nm3 / -h--500 500-500 Same oxygen concentration VOL.% 26.0 26.0 26.0 Fuel supply kg / h 63.0 63.0 63.0 Oxygen at the entrance of the second zone ° C 2000 2000 2000 Temperature Flow velocity at the entrance of the second zone m / s 426 426 426 Feedstock oil supply kg / h 140.0 140.0 140.0 Potassium concentration in feedstock ppm 0 1000 8000 Deformation of the second zone area after 2 1 mm to 1 mm to 1 mm Diameter nm 22.3 22.2 22.0 DBP oil absorption mL / 100g 205 102 79 ash% 0.03 0.23 0.94 D m 〇d nm 102 90 78 D 7 5 nm 143 132 118 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Comparative Example 5 2) Except that the axial length of the forced cooling structure part in the front part of the choke tube was set to 50 mm (the raw material oil introduction device was installed at a position of 100 mm from the choke tube inlet portion), all were used and Example 6 2 Same device 'And set the gas temperature at the inlet of the second zone to -158- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7 V. Description of the invention Carbon black is produced at (156) 2000 ° C and the potassium concentration in the feedstock is set to 1000 ppm. The manufacturing conditions and the physical properties of the carbon black produced are as shown in Table-27, and it is known that the ratio of the diameter of the aggregates to the diameter of the aggregates is larger than that of the aggregates, and the distribution of the aggregates has a broad distribution. (Comparative Example 5 3) Except for 100 mm from the entrance of the choke tube to the raw material oil introduction device, forced cooling gold and metal structures were used as the front part of the narrow part, and the rear part of the choke part was 800 mm behind the axis direction. Except for the structure of alumina refractory with a diameter of 120 mm, the same device as in Example 6 2 was used, and the gas temperature at the entrance of the second zone was set to 2000 ° C. The potassium concentration in the feedstock The production conditions and the physical properties of the carbon black produced are shown in Table 2 at 100 ppm. The production conditions and the properties of the carbon black are shown in Table 2-7. Large, and the aggregate diameter distribution is wider, and the particle size is also larger. --------------- IT ------ ^ (Please read the note on the back before filling out this page) The paper size printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Applicable to China National Standard (CNS) A4 (210X297mm) -159-536551 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (157) Zouyi 2 7 Comparative Example 52 Comparative Example 53 Fuel Air Supply Nm3 / 4l ·-500 500 Same oxygen concentration VOL.% 26.0 26.0 Fuel supply kg / h 63.0 63.0 Oxygen at the entrance of the second zone ° C 2000 2000 Temperature Flow velocity at the entrance of the second zone m / s 426 426 Feedstock oil supply kg / h 140.0 140.0 Potassium concentration in feedstock ppm 1000 1000 Deformation in the second zone after passing through 2 1 mm to 1 mm in diameter 2 nm 22.3 23.8 DBP oil absorption mL / 1 OOg 101 78 Ash% 0.22 0.20 D m 〇d nm 78 88 D 7 5 nm 110 136 (Please read the precautions on the back before filling out this page) (Examples 65 ~ 68) Set an Combustion chamber's inner diameter of 500 mm and length of 140 mm The area is connected, and a plurality of raw material nozzle ducts with an inner diameter of 60 mm and a length of 800 mm formed by the choke tube portion are introduced into the raw material introduction area 'and the atomization device is installed. The paper size is applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) -160 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7_ 5. Description of the invention (158) The inner diameter is 10 Omm, the length is 600 mm. Carbon black manufacturing furnace consisting of a control valve with a radius of 80mm. Among them, the heat transfer analysis method is performed using the furnace shown in Fig. 1- 晷 as a mold. In the figure, the straight line C is the central axis of the furnace. The part I in the figure is the part where the combustion gas flows, and the part II is the part of the refractory material. The refractory materials are composed of magnesium oxide, chrome brick, high alumina brick, thermal insulation brick, thermal insulation board, iron sheet, and so on. The furnace simulation method uses these materials as a formal mode setting. In addition, on the model of the simulated furnace, the relationship between the thermal conductivity of these materials and the temperature was investigated, and its physical properties were counted in the computer. The thermal conductivity coefficient outside the β furnace was calculated by the natural convection thermal conductivity in the computer. Parts A and B in Fig. 15 are positions where the thermoelectric pair is buried. Part A is a position of 7.5 mm from the inner wall of the furnace, and part B is a position of 220 mm from the inner wall of the furnace. By using a computer to analyze the flow and heat transfer of the gas, we know the relationship between the temperature of the gas in the furnace and the temperature of the wall of the furnace and the measurement points (points A and B). Figures 16 and 17 show this relationship. From the above, it can be known that the temperature of the furnace inner wall and the temperature of the combustion gas in the furnace can be estimated from the measurement point temperature, and the temperature of the furnace inner wall is below the refractory temperature, that is, if the temperature of the internal combustion gas is above 180 ° C Within the range of carbon black production. Other conditions are shown in Table-2. Phenol oil is used as the fuel and hydrocarbon raw materials. In Examples 6 and 68, oxygen was added to the air in order to increase the temperature of the combustion gas. In addition, the maximum temperature of the furnace material is about 1950 ° C. According to the method of the present invention, the temperature of the inner wall of the furnace can be measured at any time. Therefore, the Chinese national standard (CNS) A4 specification can be applied according to the paper size on the wall surface during operation ( 210X297 mm) _ 1fi1: &quot; --------------- IT ------ φ— (Please read the precautions on the back before filling this page) 536551 A7 B7 r_ 5. Description of the invention (159). The temperature reduces the supply of oxidizing gas or fuel at any time to reduce the temperature. In this way, carbon black can be produced at a stable high temperature while preventing the furnace wall from being damaged by heat. &gt; In Table 1 28, "the temperature of the combustion gas", "the concentration of the oxygen of the combustion gas" and "the pressure in the furnace" are measured at the point where the hydrocarbon raw material is introduced, and the temperature of the combustion gas is determined by the method The presumed concubine. "Potassium concentration" refers to the concentration of K Ο 添加 added to the hydrocarbon feedstock, and is standardized in terms of potassium concentration. Various characteristics of the obtained carbon and black are shown in Table-2. (Manufacturing Example 1) The carbon black manufacturing furnaces of Examples 6 to 5 to 8 were used to carry out the contents of Manufacturing Example 1 under the conditions shown in Table 1. When the manufacturing examples were compared with Examples 65 and 5, it was found that they had a lower temperature. Table-2 The temperature of the combustion gas in Manufacturing Example 1 in Table 8 is estimated according to the method of the present invention, and it is almost the same as the temperature measured by putting the thermoelectric pair into the furnace, so it can be confirmed that the above-mentioned estimation 値 should be correct . The physical properties of the carbon blacks printed by the employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs are shown in Table 1. When the carbon black obtained in Example 1 is compared with the carbon black obtained in Production Example 1, as shown in Table-29, the carbon black of Example 65 has a smaller particle size than the carbon black of Production Example 1. In addition, D i / 2 / Dmod is smaller and the distribution of aggregate diameter is more concentrated. D 7 5 値 is also smaller, so there are fewer substances with large aggregate diameter. In addition, it exhibits high blackness, has a low dispersion index, and has a good dispersion. -162- (Please read the precautions on the back before filling this page) The paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7B7 V. Description of the invention (160) Table 1 2 8 _ Example 65 Example 66 Example 67 Example-Ά: 68 Manufacturing Example 1 Fuel kg / H 54 5 2 ----- 54 58--5 2 Air volume Nm3 / H 520 500 470 (13) 480 (20) 500 combustion Temperature of gas ° C 1821 1820 1920 2090 1785 [1780] Oxygen concentration of combustion gas% 0.06 0.04 0.39 0.58 4.44 Flow velocity of gas choke section of combustion gas m / s 390 378 375 408 384 Supply of raw materials kg / h 55 53 59 62 65 Pressure in the furnace kg / cm3G 0.54 0.57 0.62 0.65 0.58 Potassium concentration ppm 0 800 800 800 0 Convection time in the narrow part msec 2.05 2.11 2.14 1.96 2.08 (Please read the precautions on the back before filling this page) (flow of oxygen) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs [Measurement by inserting thermoelectric pairs directly into the furnace 値] This paper size is applicable to the Chinese Standard (CNS) A4 (210X297) 嫠 -163-536551

AB V. Description of the invention (161) Table 1 2 9 __ Unit Example Example Example Example Manufacturing Example 65 66 67 68 1 Particle size nm 15 15 ... -12 11 -17 N2SA m2 / g 262 248 320 360 193 CrDBP cc / 100g 103 84 67 68 99 D m 〇d nm 43 32 29 25 68 D 1/2 nm 24 19 17 15 35 D75] im 53 41 37 31 95 Y) Ί S / Y) m 0 d 1.23 1.28 1.27 1.25 1.40 PVC blackness index 16.3 19.3 30.0 32.0 8.0 Dispersion index index 20 120 125 130 40% of feedstock oil production rate 63.6 65.4 61.3 66.2 37.2 rate of total carbon yield 32.1 33.0 32.0 34.2 19.0 D 1/2 / Dmod 0.558 0.594 0.586 0.6 0.615 (Please read the precautions on the back before filling this page) (Example 6 9) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (1) The furnace shape is set in order to have air and LPG fuel that can contain sufficient oxygen The first combustion zone of the combustion chamber with an internal diameter of 500 mm and a length of 14 mm, which is generated by the mixed combustion at a high temperature of 2 200 ° C, is connected to the first reaction zone, and runs through two branches. Nozzle capable of introducing dyed phenol oil as raw material oil into high-temperature combustion gas flow The second reaction zone area of the tube with an inner diameter of 50 mm and a length of 300 mm with an air-barrier tube portion and the size set on this paper are applicable to China National Standard (CNS) A4 (210X297 mm) -164-536551 A7 ____B7_ 5. Description of the invention (162) Downstream of the second reaction zone, the inner diameter of the reaction zone can be stopped by cooling water spraying is 10 Omm, and the length is 6 0 Omm. The furnace is a furnace-type carbon black manufacturing furnace. _ (2) Refractory materials constituting the furnace In the former furnace, the refractory materials used up to the first reaction zone and the raw material oil introduction position in the second reaction zone are magnesium oxide bricks (chemical The composition is MgO (99%), magnesia-chrome bricks (chemical composition: Mg〇66% »Cr 2 0 3 20%, F e 2 〇 3 7%), high-alumina bricks, refractory boards, and other 4-layer structures Composition; The refractory after the introduction of the raw material oil in the second reaction zone area is a high alumina refractory from the inner surface (A 1 2 0 39 9 ° / 〇, Si 2 0 · 2%, F e 2〇 30 · 2%), alumina-based ingot, refractory plate and other three-layer structure; the third reaction zone area from the inside is the aforementioned two-layer structure such as high alumina brick, alumina-based ingot, etc. Make up. (3) Dimensions of magnesia refractory. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The thickness of the magnesia brick is 50 mm, the width of the inner wall side is 70 to 100 mm, and the length is 150 to 150 mm. (1) The temperature rise and fall speed is shown in Table-30. Temperature management is performed in such a way that the temperature change of the inner wall brick is smaller than this temperature. • 165- (Please read the precautions on the back first. (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 536551 A7 B7 V. Description of the invention (163) Table 1 30 Temperature rise and fall speed of the temperature of the inner surface of the brick ~ 0 to 8 0 0 ° C 8 0 ° C / h-- 8 0 ° C / h- 800 to 1300 〇C 3 0 ° C / h 3 0 ° C / h 1 3 0 0 ° C above 8 0 ° C / h 8 0 ° C / h After the above-mentioned manufacturing furnace is continuously operated for 50 hours, the comparison between the type of the innermost refractory, the characteristics of the produced carbon black, and the manufacturing conditions is shown in Table 1 31. (Table 1 31-1 to Table 1 32-2). (Example 70) A carbon black manufacturing furnace in the shape of a 9-phase furnace similar to that of Example 6 was used, and a combustion chamber capable of mixing and combusting air containing sufficient oxygen and LPG fuel to generate a high-temperature combustion air stream at 1900 ° C was set. The refractory used was the same as in Examples 6.9. ~~ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The above-mentioned furnace is the type of innermost refractory and the carbon produced after 50 hours of continuous operation The comparison of black characteristics and manufacturing conditions is shown in Table 1 31 (Table 1 31 1 to Table 1 3 2 2). (Comparative Example 5 4) A carbon black manufacturing furnace having the same furnace shape as in Example 6 9 was used, and a combustion chamber capable of mixing and combusting air containing sufficient oxygen and LPG fuel to generate a high-temperature combustion air stream at 1750 ° C was set. The refractory used is based on the Chinese paper standard (CNS) A4 specification (210X297 mm) 536551 A7 B7__ V. Description of the invention (164) In Example 6, the whole area of the first reaction zone and the second reaction The refractory used up to the place where the raw material oil is introduced into the zone is replaced by a two-layer structure consisting of high-alumina refractories (chemical composition: A 1 2309, refractory plate) from the inner surface._ 一-After the above-mentioned manufacturing furnace has been continuously operated for 50 hours, the comparison between the type of the innermost refractory and the characteristics of the produced carbon black and the manufacturing conditions is included in Table 1 3 1 (Table 1 3 of 1) 1 to 2 of Table-32). (Comparative Examples 5 and 5) A carbon black manufacturing furnace having the same furnace shape as in Example 6 9 was used, and a mixture of air containing sufficient oxygen and LPG fuel was set to produce 190. A combustion chamber with a high-temperature combustion air stream at 0 ° C. The refractory used is the same as in Example 54. After the continuous operation of the manufacturing furnace for 50 hours, the innermost type of refractory and the characteristics of the produced carbon black The comparison of manufacturing conditions is included in Table 1 3 1 (Table 3 1 1 to Table 1 3 2 2). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Comparative Example 5 6) A carbon black manufacturing furnace with the same furnace shape as in Example 6 9 was used. Combustion chamber that can mix air containing sufficient oxygen and LPG fuel to produce a high-temperature combustion air stream at 1750 ° C. The refractory used in Example 6 and 9 is the entire first reaction zone and the second reaction zone. The refractory used up to the place where the raw material oil is introduced is changed to the chrome oxide refractory starting from the inner surface (chemical composition is Z r 0 2 95%), high oxidation -167- (Please read the precautions on the back first (Fill in this page again) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7 V. Description of the invention (165). Aluminum refractory, refractory plate and other three-layer structure. Hydrocarbon The refractory after the introduction of the raw material is the same as in Example 6. 9 After the continuous operation of the manufacturing furnace for 50 hours, the comparison between the type of the innermost refractory and the characteristics of the produced carbon black and the manufacturing conditions Shell [] one by one counted in Table One 3 1 ( 3-1 to 1 in Table 1 3 2-2). (Comparative Examples 5 7) A carbon black manufacturing furnace having the same furnace shape as in Example 6 9 was used, and one was set so that air containing sufficient oxygen could be mixed with LPG fuel for combustion. A combustion chamber that generates a high-temperature combustion air stream at 1900 ° C. The refractory used is the same as in Example 56. After the furnace has been continuously operated for 50 hours, the innermost type of refractory and its production The comparison of carbon black characteristics and manufacturing conditions are listed in Table 1 31 (Table 1 31 to 1 to Table 32 2). (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -168 · This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 536551

7 7 AB V. Description of the invention (166) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Table 3 1-1 Example 69 Example 70 Example 7 1 The main components of refractory refractory refractory refractory ( %) Mg〇99.-5- Mg〇99.5 MgO- 99.5 Fe2〇3 &lt; 0.1 Fe2〇3 &lt; 0.1 Fe2〇3 &lt; 0.1 Αΐ2〇3 &lt; 0.1 Ah 0 &lt; 0.1 Αΐ2〇3 &lt; 0 · 1 Temperature of high-temperature gas ^ rc) 1750 1900 2000 Particle size of carbon black produced 15 12 10 (nm) * 2 Amount of LPG for fuel (Nm3 / h) 10 12 14 Amount of air for combustion (Nm3 / h) 350 350 350 Oxygen concentration (%) 21 25 27 Carbon produced (kh / h) 12 16 11 Good resistance after 50 days of continuous operation (not good (not good) Cracked or dissolved)) Damage) (Please read the precautions on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 cm) -169 536551 B7 Table 1 3 1 2 Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Standards Bureau V. Description of Invention (167) Comparative Example Comparative Example Comparative Example 54 55 56 57 The innermost surface is made of refractory, high alumina, high aluminized chromium oxide, chrome oxide refractory, aluminum refractory, refractory, and refractory main components (%) AhOs 99 Ah〇3 99 Zr〇2 95 Zr〇 2 95 Temperature of high-temperature gas—re) 1750 1900 1750 1900 Particle size of carbon black produced 15 12 15 12 (nm) * 2 Amount of LPG for fuel (Nm3 / h) 10 12 10 12 Amount of air for combustion (Nm3 / h ) 350 350 350 350 Oxygen concentration (%) 21 25 21 25 Carbon produced (kh / h) 12 16 12 16 Good resistance after 50 days of continuous operation Cracks or large dissolution cracks, large cracks and dissolution) The damaged part and part fall off * 1: The temperature of the high-temperature gas in the furnace is measured with a radiation thermometer. 2: The particle size of the produced carbon black is measured using an electron microscope method. The electron microscope method is the method described below. Carbon black was poured into chloroform, and it was irradiated with 20 OKH z ultrasonic waves for 20 minutes to disperse it. The dispersed sample was fixed with a supporting film. Photograph it with a transparent electron microscope. Calculate the grain size of the paper based on the diameter of the photo and the magnification of the photo. Applicable to China National Standard (CNS) A4 (210X297 mm). 170- (Please read the Note for this page, please fill out this page) 536551 A7 B7 _ V. Description of the invention (168) diameter. This operation was performed about 15,000 times, and the arithmetic mean was used as the measurement 値. (Example 7 2 to 7 6)-Carbon blacks A to C were manufactured using the manufacturing furnace shown in Fig. 18 (a) and the manufacturing conditions shown in Table 1 32. The diameter of the choke tube portion of this manufacturing furnace is 60 mm, and the length of the choke tube portion is 700 mm. The reaction stop is in the third reaction zone area of 2000 mm in diameter provided at the outlet of the choke tube portion. At a 200 mm position of the choke tube outlet portion, the reaction was stopped by pressure spraying with water at a rate of 150 kg / hr. In Fig. 18, reference numeral 13 denotes a furnace wall. The physical properties of the carbon blacks A to C obtained are shown in Table 1 32. The "# 990" (made by Mitsubishi Chemical Corporation) of the commercial carbon black is listed in Table 1 3.2. Using this carbon black A ~ C as a master batch, the oxidation treatment was performed in the same-direction gas flow type oxidation reaction device shown in Fig. 19 (a) and under the oxidation conditions shown in Table -3. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Figure 19 The co-flow type oxidation reaction device is composed of a nitric acid gasification device, a carbon black supply / dispersion device, an oxidation reaction device, a separation device, and a separation device. The nitric acid gasification device is a device that heats air or nitrogen in the same direction as carbon black to a temperature of 100 to 150 ° C in advance, and then heats it with a heater 3 4 and introduces it into a cylinder 3 5 with nitric acid. Quantitative pump 3 6 sprays to cylinder 3 5 by pressurized spraying method to vaporize it to produce high pressure containing nitric acid • 171 _ (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) 536551 A7 __.__ B7___ 5. Description of the invention (169) · Airflow. In the figure, 37 is an air compressor. (Please read the precautions on the back before filling this page) Use a carbon black supply / dispersion device (30) with a jet disperser 3 1 to quantitatively supply the carbon black master batch to the nitrate-containing air stream obtained in this way Make it dispersed. The details of the carbon black supply / dispersion device are shown in FIG. In Fig. 20, 3 11 is a feed hopper, 3 12 is a quantitative supply device composed of a rotary valve controlled by a converter, 3 1 3 is a sprayer, and 3 1 4 is a gas ejection nozzle. The total length of the distance from the gasification device to the carbon black supply / dispersion device is 3 m (the residence time is about 0.5 seconds). The part of the sprayer that can disperse carbon black is a device with a nozzle diameter of 2mm, and the spraying speed is about 300m / s. The printed reaction device of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs uses a thermostatic bath 32 and is set at Among them, the reaction tube 33 is configured by a piping method. The constant temperature tank 32 is a device that can adjust the air temperature to 250 ° C when the residence time can be maintained within a certain range at a certain flow rate and a certain temperature range. The reaction tube is a stainless steel inner tube with an inner diameter of 25 mm and a length of 1000 m. It is bent in a spiral manner with a diameter of 1.8 to 2 mm and is set in the reaction tank. 3 9 is a hot air heater. In the device shown in Fig. 19, the reaction device is arranged in a three-base manner and can be replaced in combination. The air flow in which carbon black is dispersed is introduced into the reaction tube to perform an oxidation reaction. In the following examples, the adjustment of the residence time is changed by changing the number of consecutive reaction devices. The carbon black-containing gas stream after oxidation reaction is applied to the paper size of 10m in length. The standard of China National Standard (CNS) A4 (210X297 mm 1 -172- 536551 A7 _B7___) V. Description of the invention (170) After the inside is cooled, a separation device capable of separating carbon black and gas is introduced. The separation device 38 is a carbon black recovery method that separates carbon black from the gas stream by means of a capture filter.… Once the separated carbon black is reintroduced Detachment device. The details of the decoupling device are shown in Figure 21. The decoupling device includes a cylindrical part (390) with an inner diameter of 400mm and a height of 600nim, and an inlet filter (393) located below the cylindrical part. ), The heated air can be introduced into the heated air supply port (392) in the cylinder through the screen, and the carbon black inside the cylinder can separate nitrogen oxides and water from the carbon black in the flowing state. In Figure 21, 394 is Outlet screen, 395 is a gas outlet. In the following examples, the cylinder is charged with 1 kg of carbon black, and the air for preheating to 120 ° C is 100 liters per minute. Introduce in this way, adjust the temperature in the device to 1 2 After 0 ° C and 1-hour preheating, the temperature was raised to 150 ° C and held for 1 hour for detachment. After the carbon black cooled to 30 ° C was taken out, it was thoroughly mixed as a sample, and its physical properties and Optical suitability, etc. Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling out this page) (Manufacturing Examples 2 to 4) Using the manufacturing conditions shown in Table-3 2 Carbon black B with physical properties as shown in Table 1 2 and Mitsubishi Chemical Corporation "# 9 9 0" were subjected to co-current flow type nitric acid oxidation according to the conditions shown in Table-3 4 to obtain as shown in Table 1 3 4 The carbon black exhibits physical properties. This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 cm) -173-536551 A7 B7 V. Description of the invention (171) * (Manufacturing example 5) Use as shown in Figure 19 Co-current gas flow type oxidation device, remove nitric acid gasification device, use compressed gas generated by air compressor as raw material i, and then use co-current gas with odor-saving gas obtained by ozone generator Carbon black is oxidized and prepared with physical properties as shown in Table-3 4 Carbon black (Production Example 6) Carbon black · B 1 Og was filled in a flow column with an internal volume of 2 5 Om 1 and an ozone concentration of 0.5 · L / min was introduced into the columnar body · 1 · 6 vo 1% ozone gas, and after 24 hours oxidation treatment, it has the carbon black with physical properties shown in Table 1 34. (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -174- This paper size applies to Chinese National Standard (CNS) A4 (210X 297mm) 536551

7 7 AB V. Description of the invention (172) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Table 1 3 2 _ 黑黑 # 990 AB Volume of combustion gas (Nm2 / h) made by two and two C -750 750 750-Combustion gas Temperature (° C) 1950 1950 1950 Supply of raw oil (kg / h) 48 42 38 Potassium hydroxide (g / h) 960 920 0 • Average particle size (nm) 13.0 12.3 11.5 15.6 SEM (m2 / g) 212 233 255 182 substances cDBP (ml / 100g) 75 75 98 83 DmOd (nm) 40 37 34 45 Di / 2 (nm) 20 19 17 37 D? s (nm) 51 44 42 75 (Mg / g) 412 442 491 252 N2SA (m2 / g) 430 465 534 273 Volatile content (%) 3.2 3.6 4.0 1.2 N2SA / SEM 2.03 2.00 2.09 1.50 PVC blackness 27 27 26 15 (Please read the note on the back first Please fill in this page again for this matter) This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) _ 175-536551 V. Description of the invention (173) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 72 Example 73 Example 74 Example 75 Example 76 Base carbon black base carbon black A-carbon Black B Carbon Black C Carbon Black-B Carbon Black B Oxygen oxidation temperature (° c) 150 150 150 150 150 Chemical oxidation time (seconds) 30 30 30 30 30 Amount of conditional oxidant (nitric acid) (parts by weight) 112 112 112 80 187 Carbon black concentration (g / m2) 250 250 250 350 150 Average particle size (nm) 13.0 12.3 11.5 12.3 12.3 SEM (m2 / g) 212 233 255 233 233 cDBP (ml / lOOg) 75 75 98 75 75 Physical adsorption Amount (mg / g) 200 232 255 23 1 212 N2S A (m2 / g) 546 581 631 566 590 Volatile content (%) 21.5 22.2 24.6 20.1 27.3 Volatile content / N2SA (mg / m3) 0.39 0.38 0.39 0.36 0.46 N2SA / SEM 2.5 8 2.49 2.47 2.43 2.53 Sexual iodine content / N2SA (mg / g) 0.37 0.40 0.40 0.41 0.36 PVC blackness 29 30 32 30 30 Difference between base material and PVC blackness + 2 + 2 + 6 + 3 + 3 (Please Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 cm) _ 176-536551

7 7 AB V. Description of the invention (174) Seals of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs--34 Various acidification treatment conditions and carbon blacks ΰ Quality manufacturing manufacturing Manufacturing manufacturing Examples 2 Examples 3 Examples 4 Examples 6 Base carbon black base material # 990 riu 0m carbon black carbon black _ carbon black B BBB acid oxidation method co-directional co-directional co-directional co-directional column airflow airflow airflow strip oxidizer nitric acid nitric acid ozone ozone gas gas gas oxidation temperature (° C) 150 200 150 27 27 Oxidation time (seconds) 30 30 20 30 1440 Amount of oxidant (nitric acid) (weight 112 112 50 120 247 parts) Carbon black concentration (g / m2) 250 250 400 10 Average particle size (nm) 15.6 12.3 12.3 12.3 12.3 SEM (m2 / g) 182 233 233 233 233 cDBP (ml / lOOg) 83 75 75 75 75 Iodine adsorption amount (mg / g) 134 388 211 148 121 N2S A (m2 / g) 312 702 513 468 475 Volatile content (%) 15.8 23.0 15.2 9.7 13.8 Volatile content / N2SA (mg / m3) 0.49 0.33 0.30 0.20 0.29 N2SA / SEM 1.71 3.01 2.20 2.01 2.03 Sexual volume / N2S A (mg / g) 0.43 0.55 0.41 0.31 0.25 PVC blackness 15 27 27 27 27 There is no difference between the base material and PVC blackness &gt; 1 \\ y \ \\ 4rrr Μ / nr ΙΙΓΓ --------- Know-(please first Read the notes on the back and fill in this page.) The size of the paper is applicable to China National Standard (CNS) A4 (210X297mm) -177- 536551 A7 B7 5. Description of the invention (175). In the table, the concentration of carbon black is The weight (g) of carbon black contained in the unit isotropic gas volume (m3) in the piping of the reaction device. The oxidation temperature is the temperature of the co-current gas in the piping. The oxidation time is the average residence time of carbon black in the piping of the reaction device. The amount of oxidant is introduced in 100 parts by weight of the reacted carbon black master batch. Part by weight of oxidant. In addition, the P V C blackness difference of the masterbatch is the difference between the P V C blackness of the carbon black masterbatch obtained by the oxidation treatment and the carbon black masterbatch before the oxidation treatment. From comparison of Production Examples 3 to 6 and Example 7 3, even if the same particle size, if the volatile component / N2SA ratio is above 0.35, the blackness of PVC will increase sharply, and it can be seen that 0.35 has a critical significance. It is also known from Production Example 2 that even if the volatile component / N2SA ratio is 0.35 or more, when the particle diameter exceeds 14 nm, the blackness of PVC is not good. (Example 7-7, Manufacturing Examples 7 to 8) Printed using the manufacturing furnace of Example 7 2 to 76 in the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, and manufacturing carbon blacks D to F according to the conditions in Table 36. The physical properties of black D to F are shown in Table 1 35 (Example 7 8 and Manufacturing Examples 9 to 10). Carbon black D and E were used as master batches, and the oxidation conditions shown in Table 1 36 were used. 7 2 The same co-current air flow type oxidation device is used for oxidation treatment. -178 · (Please read the precautions on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 specification (210 &gt; &lt; 297 mm ) 536551 A7 B7 V. Description of the invention (176) The physical properties of the carbon black obtained are shown in Table 1 36. The physical properties of the commercial carbon black "FW200" (made by Texark) are listed in Table 1 3 6 (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -179- This paper size applies to Chinese National Standard (CNS) A4 (21〇297mm) 536551

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (177) Table 1 3 5 Carbon black manufacturing conditions and quality Example 77 Manufacturing Example 7 Manufacturing Example 8 ----- Carbon Black D Carbon Black E Carbon · Volume of Black F Combustion Gas (Nm2 / h) 750 250 250 Temperature of Combustion Gas (° C) 1950 1750 1750 Amount of Raw Oil (kg / h) 42 10 10 Retention Time (ms) 13 35 8 Average particle size (D) (nm) 12.3 12.1 12.2 (5 of D) / D (nm) 0.22 0.40 0.42 cDBP (ml / 100g) 75 75 75 Dm〇d (nm) 37 45 46 D1 / 2 (nm) 19 39 42 D 1/2 / D m 〇d ratio 0.53 0.86 0.91 Adsorption amount (mg / g) 412 487 186 N2SA (m2 / g) 445 641 282 SEN (m2 / g) 233 225 224 N2SA / SEM 1.37 2.85 1.26 pH 値 6.8 7.2 6.5 Toluene absorbance (%) 99 96 22 Volatile components (%) 3.6 4.3 4.2 PVC blackness 27 20 22 (Please read the precautions on the back before filling out this page) This paper standard applies to Chinese national standards ( CNS) A4 size (210X297 mm) -180 536551

7 7 AB V. Description of the invention (178) Table-36 Comparison of co-current flow type nitric acid oxidation of carbonized black and acidic carbon black Example 7 8 Manufacturing example 9 Manufacturing example 10 Carbon black, carbon black D, oxidized carbon black E, argonized mouth DEGUSSA FW700 Oxidation temperature (° C) 100 100 Oxidation time (seconds) 30 30 Concentration of oxidant (nitric acid) (parts by weight) 112 112 Carbon black concentration (g / m3) 250 250 Average particle size (D) (nm) 12.3 12.1 15.6 (D of (5) / D (nm) 0.22 0.40 0.25 D m 〇d (nm) 37 45 42 Di / 2 ( nm) 19 39 23 D 1/2 / D m 〇dt 0.53 0.86 0.55 cDBP (ml / 100g) 75 75 96 N2SA (m2 / g) 512 825 638 SEN (m2 / g) 233 225 182 N2SA / SEM 2.19 3.60 3.45 pH 値 2.5 2.4 2.0 Volatile content (%) 18.2 20.3 19.4 Specific adsorption capacity: IA (mg / g) 152 321 296 IA / N2SA (mg / g) 0.29 0.66 0.47 Volatile content +0.1 X N2SA 233 285 256 Acrylic acid Paint blackness 43 8 30 Acrylic paint gloss 15 13 15 Paint viscosity (c poise) 2400 16200 9800 PVC Degree 28 20 26 Torque of main ingredients ___ 54 92 85 Main ingredients are easy to understand _ 5 1 2 ------------ (Please read the notes on the back of the results before filling out this page) Paper size applies Chinese National Standard (CNS) A4 specification (210X297 cm) -181-536551 A7 __ · __B7_ V. Description of the invention (179) ((D-5) / D) In the table, (D-5) / D The particle size (D) and its standard error (5- in D) are obtained by measuring the particle size (electron microscope method), and then the δ of D is divided by D. (PVC black In the table, the PVC blackness is the carbon black of the present invention added to the PVC resin, dispersed with a double roller to make it flake, and the carbon black "# 40" and "# 45" of Mitsubishi Chemical Corporation. The blackness is set to 1 and 10 points, "MCF88" is 20 points, and "# 2600" is 28 points. The blackness of the sample is judged visually. (T%) 'Toluene tinting strength (T%) is determined in accordance with ASTM D-1618-8. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) (L D P E main ingredient characteristic test) The L DP E main ingredient characteristic test is performed in the following way. Under the maximum torque of the mixing ingredients of L DP E, observe the dilution state of the main ingredients in the resin after dilution, and take pictures to determine whether the dilution is good or not by observing whether they have dilution spots. Use a 2 5 0 cc spotbury mixing machine to mix 50% by weight of carbon black LDPE resin at 1 15 ° C for 10 minutes, and keep in mind that the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) _ 182 _ 536551 A / B7 V. Description of the invention (180) Record the torque change during the kneading process to obtain the maximum torque. Addition conditions LDPE resin calcium stearate edgar 1 1 0 1 carbon black sample 10 1-I 〇 10 4 8 9 g 3 9 g 8 7 g 1 5 g Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, followed by diluting carbon black with a double-roller mixer at 120 ° C for 5 minutes to make The carbon black concentration reaches 1.2% by weight. Conditions for making the diluted mixture 101.89g of LDPE resin 1.39 g of calcium stearate 1. 39 g of resin with 50% carbon black added 1. 5 g of flakes with a slit width of 0 · 3 mm A film of 6 5 ± 3 // m is made on a hot platen at 2 40 ° C. Observation was performed in an optical microscope with a magnification of 20 times, and photography was performed. In this photo, whether the main ingredient without dilution has black streaks or black particles with a diameter of 50 // or more is visually compared. If it is not found at all in the undiluted main ingredient, it is indicated by "5" When there are undiluted streaks, it will be indicated by "3", and if there are solid large particles remaining, it will be indicated by "1". (Suitability of acrylic paint) The suitability of acrylic paint (compatibility evaluation of acrylic-styrene-melamine coating system) is based on the use of acrylic-benzene paper prepared by Dainippon Coatings Co., Ltd. The size of the paper is applicable to Chinese National Standard (CNS) A4 specifications (210X297) (%) -183 · (Please read the precautions on the back before filling this page) 536551 A7 _B7___ V. Description of the Invention (181) · Ethylene-Melamine Coating Paint (Product Name: Acrylic Ester # 6 0 0 0 Crelia) With the xylene-ethylbenzene-added diluent (trade name: Acrylic acid) prepared by this company, the carbon black 2 · lg of the present invention, and paint lacquer 14. 9g, thinner 10 S · · Re-add straight for dilution · 90 g of glass beads of 2.0 mm, put it in a glass bottle with a closed inner volume of 1 40 cc, and use it together with a glass bottle containing carbon black as a reference After dispersing in a paint disperser made by Ryd Peel Co., Ltd. for 240 minutes, the upper layer clear coating dispersion test solution 3.0 g was taken, and the viscosity was measured with an E-type viscometer made by TOKIME. The remaining dispersed paint in each glass bottle was further added with 51.4 g of paint paint, and dispersed in 5 minutes, and an appropriate amount of the upper liquid of the paint test solution was taken. This coating is arranged on a smooth PET film, and then uniformly coated with a 27 mill smear for 30 minutes to achieve a uniform ride thickness. After standing at room temperature, the coating-coated film is left at a temperature level. After grilling in a thermostatic bath at 120 ° C ± 10 ° C for 30 minutes, take it out, and after cooling, visually judge the blackness and gloss of each coating film. The standard for each judgment is 10 points for carbon black "# 2650" made by Mitsubishi Dental Corporation, and printed by DEGUSSA "carbon black for employees of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) "FW 2 0 0" is 30 points, etc., and the gloss is based on "# 2650" as 10 points, and "FW200" as 15 points as the reference point to visually judge the blackness of each coating film sample. The carbon black C of Production Example 7 had (D-5) / D exceeding 0.35, N2SA / SEM exceeding 2.8, which was less than 0.35 compared to (Dδ) / D, and N2SA / SEM was 2 · 8 or less. The pv C blackness of the embodiment is low. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -184 · 536551 A7 __ ___B7_ V. Description of the invention (182) In manufacturing example 9, if it is to be subjected to oxidation treatment to make the pH 2 2 · 5 or less, and when applied to acrylic paints, (d δ) / D exceeds 0 · 35, N2SA / SEM exceeds 2.8, and the δ of this point and D is 0.35 or less, and N2SA / S-EM is 2 · Implementation of the following 8] [1: [: @, the acrylic paint viscosity increased significantly, and the acrylic paint blackness is also low, the PVC blackness is also low. In Production Example 8, (5 of D) / D exceeded 0.35, and when compared with the examples in which D 5 was 0.35 or less, the blackness of PVC was low and the absorbance of toluene was also low. In Production Example 10, N2SA / SEM exceeds 2 · 8, which is higher than the embodiment in which the acrylic viscosity is N2SA / SEM is 2 · 8 or less, and the thickness of the acrylic coating is lower than in the embodiment in which N2SA / SEM is 2 · 8 or less. In addition, the torque of the main ingredients is also high. (Example 7 9 ~ 8 3) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The schematic diagram is shown in Figure 18, and the use is the same as in Example 7 2 The manufacturing furnace 'produces carbon black G according to the manufacturing conditions shown in Table-37. The physical properties of carbon black g are shown in Table 1 37. This carbon black G and carbon black B described in Table-32 were used as master batches, and oxidation treatment was performed according to the oxidation conditions shown in Table-38. The physical properties of the obtained carbon black are shown in Table 1-38. (Comparative Examples 5 8 to 6 1) The physical properties of various carbon blacks sold in the market are shown in Table-39. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). ^ 5. '&Quot; 536551 A7 B7 V. Description of the invention (183) · (Manufacturing Examples 1 1, 12) Use of commercial carbon black "# 2600 "(Mitsubishi Chemical Corporation i) and carbon black B as master batches, and oxidation treatments are performed according to the chemical conversion conditions shown in Table-40. The physical properties of the obtained carbon black are shown in Table 1 40. Table—3 7 Manufacturing conditions and physical properties of carbon black base material (base material) Manufacturing conditions Volume of combustion gas (Nm3 / h) 7 5 0 Temperature of combustion gas (° C) 19 5 0 Amount of feedstock oil (kg / h) 6 2 Potassium hydroxide (g / h) 2 16 0 Average particle size (nm) 15.0 CDBP (ml / 100g) 6 6 Dm〇d (nm) 4 4 D i / 2 (nm) 2 4 D? S ( nm) 5 5 Tablet adsorption amount (mg / g) 2 7 7 N2SA (m2 / g) 2 9 3 Volatile components (%) 1.8 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) Please fill in this page again for this matter) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -186-536551 7 7 A η 5. Description of the invention (184) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 3 &quot; 3 8 Oxidation conditions and properties of carbon black in co-current flow nitric acid argonization method Example 79 Example 80 Example 81 Example 8 Example 83 Carbon black base carbon black carbon black rMi carbon black carbon black B GG Β Β Oxidation temperature (° c) 150 150 150 150 150 Chemical oxidation time (seconds) 30 30 30 30 30 CB nitric acid (wt%) 1 12 112 112 80 187 pieces Particle concentration (g / m3) 250 250 250 350 150 Average particle size (nm) 15.0 15.0 12.3 12.3 12.3 Dm〇d (nm) 45 45 37 36 37 Compound Di / 2 (nm) 24 24 20 19 20 D75 (nm) 54 55 47 45 46 D 1/2 / D m 0 d ratio 0.53 0.53 0.54 0.53 0.54 D75 / E) mod t 1.20 1.22 1.27 1.25 1.24 cDBP (ml / lOOg) 66 66 75 75 75 N2S A (m2 / g) 329 -— 352 576 581 592 Volatile content (%) 13.2 16.7 20.5 22.2 23.1 Volatile content / bhSA (mg / m2) 0.40 0.47 0.36 0.38 0.39 Iodine adsorption capacity: IA (mg / g) 152 142 223 232 252 IA / N2SA (mg / g) 0.46 0.40 0.39 0.40 0.43 Volatile content +0.1 x N2SA 165 202 263 280 290 Acrylic paint blackness 30 30 45 45 45 Acrylic paint gloss 15 15 15 15 15 Paint viscosity (c poise) 1900 2000 2000 2100 2000 (Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 cm) -187- 536551 A7B7 V. Description of the invention (185) Table-3 9 The nature of various acid carbon blacks Black is a powdery substance) Comparative Example 58 Comparative Example 59 Comparative Example 60 5Γ Comparative Example 6 Carbon black DEGUSSA CABOT Mitsubishi Chemical Mitsubishi Chemical Corporation FW200 Corporation M1300 School # 2650 # 2350 Average particle size (nm) 15.6 11.5 13.0 15.2 Dm〇d (nm) 42 32 37 41 Di / 2 (nm) 23 27 29 88 D? s (nm) 51 315 85 398 ID 1/2 / Dmod ratio 0.55 0.84 0.78 2.15 D 7 5 / D m 〇d ratio 1.21 9.84 2.30 9.71 cDBP (ml / lOOg) 96 79 48 43 N2SA (m2 / g) 628 595 419 581 Volatile content (%) 19.4 16.5 8.5 7.5 Volatile content / N2SA (mg / m2) 0.31 0.28 0.24 0.26 True adsorption amount: IA (mg / g) 296 400 185 156 IA / N2SA (mg / g) 0.47 0.67 0.51 0.40 Volatile content +0.1 x n2sa 257 224 121 104 Acrylic paint blackness 30 20 10 6 Acrylic paint gloss 15 10 10 7 Coating viscosity (c poise) 9800 8200 2800 2200 (Please read the notes on the back before filling out this page) -188- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 536551 A7B7 V. Description of the invention (186) Oxidation conditions and properties of carbon black in the airflow nitric acid oxidation method Example 1 2 Carbon black base material # 2650 Carbon fuming oxygen oxidation temperature fc) 150 150 Chemical oxidation time (seconds) 30 30 Concentration of oxidant (nitric acid) (weight 112 56 pieces) Particle concentration (g / m3) 250 500 average Particle size (nm) 13.0 12.3 DmOd (nm) 37 37 Di / 2 (nm) 29 20 D75 (nm) 85 47 D 1/2 / ID m 0 dt 0.78 0.54 D75 / Dmod ratio 2.30 1.27 CdBP ( ml / lOOg) 48 75 N2S A (m2 / g) 419 594 Volatile content (%)-17.6 18.6 Volatile content / N2SA (mg / m2) 0.42 0.31 Iodine adsorption capacity: IA (mg / g) 185 295 IA / N2SA (mg / g) 0.44 0.40 Volatile ingredients +0.1 x N2SA 218 202 Acrylic paint blackness 18 * 35 Acrylic paint gloss 10 13 Paint viscosity (c poise) 2000 5500 (Please read the precautions on the back before filling this page) Ministry of Economy When printing the carbon blacks of these examples with the carbon blacks of the comparative examples and examples printed by the Consumer Standards Cooperative of the Central Bureau of Standards, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -189-536551 A7 B7 _ V. Description of the invention (187) · Particle size below 16 nm and D1 / 2 / D ^ d is When 1.6 or less, a volatile component product of the unit area (lines with "volatile component / N2SA" table) or higher of 0 · 35 material, when compared to not having substance ΐ the plurality of properties, the various optical suitability is also preferred. …, (Example 8 4) Carbon black made by Mitsubishi Chemical Corporation, with an average particle size of 13 · nm, N2SA specific surface area of 370 m2 / g, CrDBP oil absorption of 48ml / 100g, and volatile content of 2.1 wt% "# 2 6 0 0" was used as a master batch for oxidation treatment. The oxidation treatment uses an oxidation device as shown in FIG. 19. Specifically, the nitric acid gas concentration of 98% concentrated sulfuric acid gasified in the air is 8 · Ονο 1% nitric acid-containing gas, preheated at 150 ° C, and the temperature in the reaction device is controlled to 15 Next, it was introduced into the reaction device at a flow rate of 10 m / sec. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). This airflow contains the quantity provided by the carbon black supply / dispersion device shown in Figure 19 at 5 6 g / min. The nitric acid concentration of 100 parts by weight of carbon black was 91 parts by weight, and the oxidizing reaction was carried out within 30 seconds of being dispersed in a gas stream by an ejector so as to be retained in a reaction device. Secondly, the air flow in which the carbon black is dispersed is cooled to 50 ° C, and the carbon black is separated from the gas using a capture filter. The obtained carbon black 1 kg was treated by a flow-type desorption apparatus shown in Fig. 21 and desorbed. The carbon black after detachment has a volatile content of 18.2wt%.

The specific surface area of N2SA is 403m2 / g, and the volatile content / N2SA is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). "190 · 536551 A7 B7_ V. Description of the invention (188) The ratio is 0 · 45mg / m2, pH 値 2 · 2, NOx amount is 75 P pm (N Ox content of carbon black before detachment is 4 6 0 0 p pm) 〇 (Example 8 5) Except for the nitric acid-containing gas to be introduced into the reaction device The nitric acid concentration was set to 10 · Ονο 1%, and the nitric acid concentration of 100 parts by weight of carbon black was 1 12 parts by weight, and the other operations were performed in the same manner as in Example 84. The resulting volatile components of the carbon black after the release operation were volatile components. It is 20.7 wt%, the specific surface area of N2SA is 405m2 / g, the ratio of volatile components / N2SA is 0.5 mg / m2, the pH is 2 · 2, and the amount of NOx is 7 2 ρ pm. (Example 8 6) The carbon black in the reactor was set to a reaction time of 20 seconds, except that the oxidation reaction was performed in the same way as in Example 84. 4. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) (Fill in this page) The volatile content of the carbon black obtained after the release operation is 16. 8 wt ° / 〇 The specific surface area of N2SA is 396m2 / g, the ratio of volatile components / N2SA is 0 · 42mg / m2, pH 値 2 · 2, and the amount of Nox is 8 1 ρ pm. (Example 8) An average particle size of 23 · 4nm, N2SA specific surface area 1 2 6 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm). 191 · 536551 A7 _ __B7_ V. Description of the invention (189) * m2 / g, volatile content 0.6 wt% of Mitsubishi Chemical company's carbon black "# 4 7" is used as a master batch for oxidation treatment. The oxidation treatment uses an oxidation device as shown in Fig. 19. Specifically, the nitric acid gas containing 70% concentrated sulfuric acid gasified in the air with a nitric acid concentration of 5 · Ονο 1%, was preheated at 100 ° C, and the temperature in the reaction device was controlled at At 100 ° C, it was introduced into the reaction device at a flow rate of 10 m / sec. This air stream contains a nitric acid concentration of 15 parts by weight to 100 parts by weight of carbon black provided by the carbon black supply / dispersion device shown in FIG. 19 at a quantity of 240 g / min and dispersed by an ejector. In a gas stream, the oxidation reaction was performed within 20 seconds of staying in the reaction device. Secondly, the airflow in which the carbon black is dispersed is cooled to 50 ° C, and the carbon black is separated from the gas using a capture filter. The obtained carbon black 1 kg was treated by a flow-type desorption apparatus shown in Fig. 21 and detached. The carbon black after detachment has a volatile content of 3.6% by weight, a specific surface area of N2SA of 12 6m2 / g, a ratio of volatile components / N2 SA of 0 · 29mg / m2, a pH of 3 · 2, and an amount of NOx of 31. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the precautions on the back before filling this page) ppm 〇 'The fluidity of the inks with these carbon blacks dispersed is 5 3 7mm / time. (Embodiments 8 8, 8 9) The same operations were performed according to Embodiment 8 7 except that the conditions were as shown in Table-43. The physical properties of the obtained carbon black are shown in Table 1 4 3 &amp; Zhang Niu applicable towel SS home turn (CNS) (21GX297 mm) ΤΤοΤΙ 536551 A7 _B7 V. Description of the invention (190) (Please read the precautions on the back before Fill in this page) (Manufacturing example 1 3) Substitute the nitric acid-containing gas with an ozone concentration of> 4 ... · 6 v 〇1% -ozone-containing gas, and perform oxidation treatment in accordance with the conditions shown in Table 41. The other operations are the same as those in Example 84. Various physical properties of the obtained carbon black are shown in Table 1 41. (Manufacturing Example 1 4) Except for the conditions shown in Table-41, various conditions were the same as those in Example 84. The gas used for the oxidation treatment is a gas having a nitrogen dioxide concentration of 10 · Ονο 1%. Various physical properties of the obtained carbon black are shown in Table 1 41. (Manufacturing example 15) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, put 500 g of "# 2600" and 70 g of dilute nitric acid 500 g in a super kneader and mix it at 1000 rpm, then charge it fully (2) In the fluidized bed type detachment device shown in Fig. 21, the air preheated to 150 ° C is introduced at 1000 liters / min. At the same time, the temperature of the gas in the device is adjusted to 150 ° C. 3 Carbon black was prepared after leaching for 1 hour and cooling to 30 ° C. The prepared carbon black has a volatile content of 11.5 wt%, a specific surface area of N2SA of 422 m2 / g, a ratio of volatile components / N2SA of 0 · 27mg / m2, a pH of 2 · 2, and an amount of NOx of -193- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 536551 A7 B7 V. Description of the invention (191) 1 1 8 p pm, and the shape is almost hard particles, and the hardness of the particles is 3 5 · 4 g weight. (Manufacturing example 16) ···--In a rotary kiln with a stirring wing of 3 5 Omm in diameter and 40 Omm in length installed in a heating furnace, "# 2 6 0 0" 5 00g In the 15 r pm rotation, adjust the internal temperature of the kiln to a state of 15 CTC ± 20 ° C, 70% nitric acid at a ratio of 10 g / min for 30 minutes, and 100 parts by weight of carbon black as 40 parts by weight of nitric acid was sprayed to the central part of the kiln by a pressure spray nozzle for oxidation, and then air was introduced into the kiln at a rate of 200 liters / minute in 60 minutes to carry out the residual nitrogen oxides. Of it. The prepared carbon black has a volatile content of 15.2% by weight, a specific surface area of N2SA of 4 8 3m2 / g, a ratio of volatile components / N2SA of 0.31 mg / m2, a pH of 2 · 2, and an amount of Nox of 86 P pm, and some hard particles 颗粒 exist, the hardness of the particles is 2 7 · 2 g. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) (Manufacturing Examples 17 and 18) Except for the processing conditions according to the conditions shown in Table-4 2, the rest are based on the examples 8 4 Do the same. Various physical properties of the obtained carbon black are shown in Table-4 2. (Manufacturing Examples 1 and 20) The paper size is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) -194 _ 536551 Α7Β7 V. Description of the invention (192) Except the processing conditions according to the conditions shown in Table-4 3 Otherwise, the same operations are performed according to Embodiments 8 and 7. The same-direction gas for oxidation treatment used in Production Example 19 was the same as in Example 87, and was obtained by vaporizing concentrated nitric acid. The same-direction oxidation-treatment gas used in Production Example 20-a gas having a nitrogen dioxide concentration of 1 0 · 0νο 1%. Various physical properties of the obtained carbon black are shown in Table 1 43. It can be known from the above embodiments and manufacturing examples that in a mixed gas stream containing gaseous nitric acid, an oxidation treatment is performed by contacting the carbon black with nitric acid gas in a dispersed state with a gas stream having a gas flow energy capable of dispersing carbon black. , Can solve the problem of carbon black consolidation and formation of hard particles. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, Table 1 4 1 Mitsubishi Carbon Black # 2600 after oxidation with various oxidants Example 84 Manufacturing Example 1 3 Manufacturing Example 14 Manufacturing Example 1 6 # 2600 oxidant type nitric acid ozone gas nitrogen dioxide nitric acid (liquid) Μ oxidation device co-current air flow co-current air flow 1 co-current air flow g-carbon black concentration 250g / m3 10g / m3 __ 20g / m3 •-oxidant amount 91 105 220 40 氺 1 Oxidation temperature 150 ° C 27 ° C 150 ° C 150 ° C • Reaction time 30 seconds 30 seconds 30 seconds 30 minutes • Volatile components 18.2% 10.2% 11.6% 15.2% 2.1% N 2 SA 403m2 / g 368m2 / g 407m2 / g 483m2 / g 370m2 / g Volatile components 0.45 0.28 0.29 0.31 0.06 / N 2 SA Hard particles Μ ΙΓΓ J \\\ j \\\ Presence * 1 is 100 parts by weight of carbon black. -195- This paper size is applicable to the national standard (CNS) A4 specification (210X297 cm) 536551 A7 B7 V. Description of the invention (193) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Properties of oxidized acid strip f and carbon black Example 84 Example 85 Example 86 Manufacturing Example 17 Manufacturing Example 18 Base # 2600 # 2600 # 2 谦 # 2600 # 2600 Carbon black concentration 250g / m3 250g / m3 250g / m3 250g / m3 250g / m3 Nitric acid concentration 8% 10% 10% 10% 10% Nitric acid amount * 1 91 112 112 112 112 Oxidation temperature 150 ° C 150 ° C 150 ° C 100 ° C 100 ° C Reaction time 30 seconds 30 Second 20 seconds 30 minutes 20 seconds Volatile content 18.2% 20.7% 16.8% 13.1% 13.0% N 2 SA 403m2 / g 405m2 / g 396m2 / g 391m2 / g 389m2 / g Volatile content / N 2 SA 0.45 0.51 0.42 0.33 0.36 * 1 It is 100 parts by weight of carbon black. (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -196-536551

7 7 AB Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Description of Invention (194) Table 1 4 3 Mitsubishi Carbon Black # 4 7 Co-flow Air Oxidation Process Example 87 Example 88 Example 89 Manufacturing Example 19 Manufacturing example.-20 Base material # 47 # 47 # 47… · # 47 # 47 Oxidant species nitric acid gas nitric acid nitric acid nitric acid nitrogen dioxide carbon black concentration 950g / m3 950g / m3 1400g / m3 950g / m3 250g / m3 Nitric acid / n〇2 Concentration 5% 5% 5% 5% 10% Oxidant amount 15% 15% 15% 15% 110% Oxidation temperature 100 ° c 70 ° C 100 ° c 150 t 100 ° C Reaction time 20 seconds 20 seconds 20 seconds 20 minutes 30 seconds Volatile content 3.6% 3.1% 2.7% 3.4% 3.0% N 2 SA 1 26m2 / g 126m2 / g 126m2 / g 138m2 / g 14 1 m2 / g Volatile content / N 2 SA 0.29 0.25 0.21 0.25 0.21 Static flow of ink 537mm 634mm 218mm 85mm 12mm * 1 is 100 parts by weight of carbon black. (Hardness of Granulated Particles) "The method for measuring the hardness of granulated particles" is measured in accordance with J I S K 1 5 1 0-8 8 b. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 cm) 197 · --------- Free | (Please read the precautions on the back before filling out this page 536551 A7 B7 V. Description of the invention ( 195). (P Η 値) The measurement method of P Η 値 is determined in accordance with ASTMD — 1 5 1 ί — 8 4.... (N OX content) printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please Read the precautions on the back before filling this page.) Add 50 ml of 0.05% by weight nitric acid aqueous solution containing 1.0 g of carbon black into the flask and stir with a stir bar for 30 minutes to dissolve NOx in the carbon black. The carbon black was separated from the upper clarifying solution with a centrifugal separator. To 20 ml of the above clarifying solution, sulfonamide containing sodium hydroxide and acetic acid, which had been adjusted to pH 値 7.0 · ± 0.1 · 1, was added. 0 · 1933mo 1 / L 15 ml of aqueous solution and 0.5 g of zinc powder were added to pure water to make the whole volume reach 100 m 1 and mixed for 1 minute. After the mixture was filtered through filter paper, the filtrate 20 m 1 was taken and 20% by weight of hydrochloric acid was added. After adding 3 ml of an aqueous solution and 1 ml of a 0.1% by weight N-1 naphthaleneethylenediamine solution, add Pure water with a volume of 25 m Γ is mixed and allowed to stand for 15 minutes at 15 to 30 ° C. After standing, it is moved to a quartz absorbance measurement chamber to adjust the absorbance to a wavelength of 5 4 5 nm. Measure the absorbance with a measuring meter, and use three kinds of potassium nitrate solutions of known concentrations prepared in advance to determine the absorbance and the regression formula for the correction of nitrogen dioxide (N 0 2) concentration in a centrifugal operation to determine the concentration of the solution. N 0 2 concentration, with No 2 concentration (p pm) = No 2 concentration of the measurement solution X 5 0/2 0 This paper size is applicable to China National Standard (CNS) 8 4 specifications (210X297 mm) -198- 536551 A7 __B7_ V. Description of the invention (196) The determination of the concentration of N 0 2 in carbon black. (Still fluidity of ink) Use of phenol tree-resin made by Showa Paint Co., Ltd .: MS-8 0 0-38 · Og and alkyd resin: F—1042 · 0g is mixed with 5.7g of No. 6 solvent made by Japan Petroleum Corporation and mixed with a stirring rod to make a mixed paint. 45.7g of mixed paint and 20 · Og of carbon black are made of polyethylene Mix in a cup and place it in a 3-roller kneader. Repeat the kneaded ink 3 to 7 times with 50 beads. Disperse it to a degree of dispersion below 10 to make a disperse ink. Use this disperse ink 20 · Og and mixed paint 23 · 8g in a 3-roll kneader and mix 3 times before adding 7 · 6 4 g of No. 6 solvent, kneaded 3 times to make ink. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Use the ink 2.0 g and 0 · 2 8 g of solvent No. 6 on the glass plate and mix with the ointment for 3 minutes. 0.7 ± 0 · lg of ink was placed on the top of a horizontal smooth glass plate. In this state, it was left to stand for 3 hours at 25 ° C ± 5 ° C. After the glass plate was erected for 1 hour, the ink flow was measured. length. [Industrial Applicability] When the carbon black of the present invention is used as a black pigment in resin colorants, printing inks, and coatings, it can solve the problem that conventional blackness and dispersibility cannot be obtained, and improve productivity. In addition, it can prevent degradation when used in resin composition, and can improve abrasion resistance when used as rubber composition. As a coating group, this paper applies Chinese National Standard (CNS) A4 specification (210X297 cm) · 199 · 536551 A7 _ · _B7____ 5. Description of the Invention (197) It can prevent the phenomenon of aggregation when it is finished, so it is a carbon black with extremely high safety. Therefore, it is an extremely useful ingredient for making resin colorants, coatings, and rubber compositions. In addition, the production of carbon black can also be carried out under continuous high temperature and stability, and the aggregate diameter distribution is extremely concentrated. In addition to the carbon black with significantly reduced ash content, it is also possible to efficiently and continuously produce high carbon black. Quality carbon black. If the carbon black of the present invention is used as a black pigment in resin colorants, printing inks, and coatings, it can obtain a high degree of blackness that has not been obtained in the past. A substance that has both darkness and dispersibility, and has an industrial price. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -200- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

536551 Patent Application Scope A8 B8 C8 D8 .JI Second Patent Application No. 87 1 1 4372 Chinese Patent Application Amendment (please read the notes on the back before filling this page) Amendment on January 30, 1992 1. A carbon black, which The average particle diameter is 13 nm or less, D_d is 80 nm or less, the Di / 2 / Dni0d ratio is 0.6 or less, and pH 値 is 5 or more. 2. If the carbon black of item 1 of the patent application scope, its Di / 2 / ratio is 0.5 5 or less. 3. If the carbon black of item 1 or 2 of the patent application scope, its D 7 5 / Dmod ratio is 1 · 6 or less. 4. If the carbon black of item 1 or 2 of the patent application scope, its D 7 5 / Dm0d ratio is 1.3 or less. 5. If the carbon black of item 1 or 2 of the patent application scope, its D B_ P / D_d is 3.4 or more. 6. A kind of carbon black with an average particle diameter of 14 nm or less, a ratio of N2SA / SEM specific surface area of 1.3 or more, a pH value of 5 or more, and a cDBP of 50 cc / 100 g or more. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 7. If the carbon black in the scope of the patent application is No. 6, it is less than 80 nm. 8. If the carbon black of item 6 or 7 of the patent application scope, its D: / 2 / Dmod ratio is 0.6 or less. 9. If the carbon black of item 6 or 7 of the patent application scope, the D i / 2/0 ^ ratio is 0.5 5 or less. This paper size is applicable to Chinese National Standard (CNS) A4 specification (2) 0 × 297 mm 536551 A8 B8 C8 D8 VI. Application for patent scope 1 10. For carbon blacks with scope of patent application No. 6 or 7, its DBP / D— It is 3 · 4 or more .. (Please read the precautions on the back before filling this page) 1 1 · A carbon black with an average particle size of 13 nm or less, a ratio of N2SA / SEM specific surface area of 1.3 or more, and pH 値 of 5 or more. &gt; 1 2. The carbon black according to item 11 of the scope of patent application, which is 80 nm or less. 1 3. If the carbon black in the scope of patent application No. 11 or 12 has a D 1/2 / D-ratio of 0.6 or less. 14. If the carbon black in the scope of patent application No. 11 or 12 has a D ι / 2 / Dn ^ d ratio of 0.55 or less. 1 5. If the carbon black in the scope of patent application No. 11 or 12 has a cDBP of 50c c / 100g or more. 16. For carbon blacks in the scope of claims 11 or 12, the D B P / DmDd is 3 · 4 or more. 17. — A kind of carbon black with an average particle diameter of 13 nm or less, N2SA of 200 m2 / g or more, DmOd of 80 nm or less, and a D i / 2 / D ^ d ratio of 0.6 Hereinafter, P Η 値 is 5 or more. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 18. If the carbon black in item 14 of the patent application scope, its D Β P is above 70cc / 100g. 19. If the carbon black of item 9 or 10 of the scope of patent application, its D 7 5 / D ^ d ratio is 1.6 or less. 2 0. If the carbon black in the scope of patent application No. 17 or 18, its D B P / D— is 3.4 or more. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -2-536551 A8 B8 C8 D8 VI. Patent application scope 2 1 · — Carbon black, DBP / above 3 · 4, Dm 〇d It is 80 nm or less. (Please read the precautions on the back before filling out this page) 2 2. If the carbon black in item 21 of the patent application scope, it is less than 40 n m. 2 3 · If the carbon black in item 21 of the patent application scope, its D: / 2 / Dn ^ d ratio is 0 · 6 or less. 2 4 · If the carbon black according to any one of the scope of patent applications Nos. 21 to 23, the average particle diameter is 13 nm or less. 2 5 · If the carbon black in any of the items 21 to 23 of the scope of patent application has a pH of 5 or higher. 2 6 · If the carbon black in any one of the scope of patent applications Nos. 21 to 23, its D B P / D—is 3.4 or more. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 ·· A method for manufacturing carbon black, which is formed by mixing the high-temperature combustion gas stream with the hydrocarbon raw material in the first reaction zone area formed by the high-temperature combustion gas stream. A method for producing carbon black by using a furnace for manufacturing carbon black, including a second reaction zone region having a gas barrier tube portion, and a third reaction zone region located downstream of the second reaction zone region to stop the reaction, characterized by using a gas barrier tube The length is more than 800 mm, and the oxygen concentration in the combustion gas at the introduction site of the hydrocarbon raw material is 3 v 〇1% or less. 28. The method for manufacturing carbon black according to item 27 of the scope of patent application, wherein the diameter of the choke tube portion is 170 mm or less, and the flow velocity of the combustion gas inside the choke tube is 250 m / s or more. 2 9 · If the method of manufacturing carbon black in the scope of patent application No. 27 or 28, the turbulent mixing speed of the introduction part of the hydrocarbon raw material is based on the Chinese paper standard (CNS) A4 specification (210X: 297) (Mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 536551 A8 B8 C8 D8 6. The scope of patent application is above 120 / S. 3〇. — A kind of carbon black, which is a carbon black produced by a manufacturing method of any one or more of the scope of patent application Nos. 27 to 2-9, and has an average particle diameter of 25 nm or less, Di / 2〆D —Ratio is 0.6 or less' D 7 5 / ratio is 1.3 or less. 31. The carbon black of item 30 in the scope of patent application has an average particle diameter of 20 nm or less. 3 2 · If the carbon black in the scope of patent application No. 30 or 31, its dispersion index is below 150. 3 3 · If the carbon black in the scope of patent application No. 30 or 31, its DBP / Dm0d is 3.4 or more. 3 4. A carbon black which is a carbon black produced by a manufacturing method of any one or more of items 27 to 29 in the scope of patent application, and its Dm. (3 is 50 or less, and the average particle size is 25 nm or less. D1 / 2 / ratio is 0 or less. 3 5 · If the carbon black of the scope of patent application No. 34, its DBP / D m. D is 3 · 4 or more. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this page) -4-