PL108421B1 - Method of generating furnace black - Google Patents

Description

The subject of the invention is a process for the production of expanded structure furnace black, used mainly as a filler, pigment and reinforcing agent for rubber and plastics. Usually, the carbon black furnace process consists in cracking and / or incomplete combustion of a hydrocarbon feedstock such as as natural gas or cyclic hydrocarbons in a closed conversion zone at a temperature above 982 ° C. The carbon black entrained in the gases emitted from the conversion zone is then cooled and collected by suitable equipment, usually used in the art. Polish Patent No. 61215 describes a method of producing carbon black by burning hydrocarbons in a three-chamber furnace at using a gas containing free oxygen, a characteristic feature of the process that 15-70% by weight of the oxygen introduced into the first two chambers is fed into the first chamber. It is stated in this specification that the structure of the carbon black can be varied by varying the feed point of the hydrocarbon feed along the axis of the first chamber. British Patent No. 1,359,216 teaches a process for producing carbon black at high speed and good yields. This method may be briefly described as a zoned process. In the first stage of this process, the liquid fuel burns in the presence of air. Thereafter, the speed of the gaseous combustion product obtained in the first stage is increased, and a raw material containing coal is injected into the flue gas stream in a substantially transverse direction. The resulting mixture is held in another closed zone for a period of time sufficient to form soot, after which it is cooled to isolate the product. However, it is very difficult and practically impossible on an industrial scale to produce furnace carbon black with a structure higher than that obtained in so far from any raw material. The method according to the invention makes it possible to produce a carbon black having a higher structure than that obtained by the known method, which is indicated in particular by the unexpected increase in the adsorption of butyl phthalate (DBP). The carbon black obtained by the method of the invention is also characterized by good reinforcing properties, and the rubber mixtures containing these carbon blacks have a low value of shrinkage after extrusion. In the method of the invention, carbon blacks with such a surprisingly high structure are produced by introducing into the zone of a substantial reaction In the zone black production process described below, a specific amount of auxiliary liquid or gaseous hydrocarbon. The method according to the invention consists in that, in a first step, the fuel and oxidant are reacted to form a stream of hot flue gases of 20 108 421 108 421 3 sufficient energy to convert into soot a liquid hydrocarbon feed from which the soot is formed, which stream then passes at a high linear rate to the second stage where the liquid hydrocarbon feed is injected into it in the form of a plurality of coherent jets of essentially transversely to the flow direction of the gas stream and under sufficient pressure to obtain the degree of penetration required for proper shearing and mixing. In the third stage, the hydrocarbon raw material is decomposed and transformed into carbon black. An auxiliary hydrocarbon is introduced at the point referred to as the "primary reaction zone" in such an amount that its carbon content is 2 to 60% by weight, based on the total carbon content of the reactants. The reaction is terminated by cooling, then separating and recovering the carbon black. Auxiliary liquid or gaseous hydrocarbon is introduced into the carbon black process of the present invention in any suitable manner. The term "principal reaction zone" denotes this zone in the carbon black production process. the previously introduced mixed, atomized and vaporized hydrocarbon feed is now undergoing the main carbon black formation reactions, forming soot nuclei. More specifically, the "primary reaction zone" in the method according to the invention refers to the point downstream of the hydrocarbon injection site 30 from which the soot is formed in the flow direction at a distance of 2 to 60% of the separation between the hydrocarbon injection site and the soot site. In the process of the invention, auxiliary hydrocarbon is injected into the gas stream to be treated in any way, such as, for example, in an axial or transverse direction of the gas stream. Moreover, it does not really matter where in the process. the auxiliary hydrocarbon is introduced on the condition that it enters the primary reaction zone practically unreacted, i.e. without any soot particles formed. Preferably, the auxiliary liquid or gaseous hydrocarbon is introduced into the carbon black process at a point in the direction of the carbon black. downstream of the point of injection of the hydrocarbon feed into the stream high speed 50 exhaust gas. It is important whether the auxiliary hydrocarbon is introduced in liquid or gaseous form, and the amount of auxiliary hydrocarbon used also influences the properties of the product obtained. 55 The term "structure" in reference to carbon black describes the original property of the carbon black, which is not influenced by any property or set of properties. The term flax is generally used in the art to describe the agglomeration extent of primary carbon black stocks. As all judges show some degree of agglomeration Particle soot, individual carbon blacks are classified as low, normal or high structure carbon black depending on the relative degree of aggregation.The boundary between low, normal and high structure carbon blacks is usually not clearly defined. The structure of the carbon black is considered to be high, when there is a strong tendency for the particles to bind into chains. On the other hand, the soot structure is too low, when there is a weak tendency to agglomerate the original particles. The soot structure is determined by the oil adsorption method using butyl phthalate, which is carried out according to ASTM-D-2414-72. The relationship between the carbon black structure and the properties of with lines of rubber mixtures containing individual soot. This dependence is sometimes described as advantageous, since the growth of the carbon black structure makes it easier to extrude rubber mixtures containing the carbon black and they are characterized by low shrinkage values after pressing. This relationship is also referred to as the effect of the degree of structure of the carbon black on the module of rubber mixtures containing a specific carbon black. In this case, it is generally accepted that the use of high structured carbon black to compound rubber compounds with a high modulus, while the use of low structure carbon black results in low modulus blends. Since the invention relates to a method for producing furnace carbon black with a much higher structure than before, it was examined whether the above-mentioned relationships are true. By producing carbon blacks with a much higher structure, it was found that their incorporation into natural rubber and synthetic rubber mixtures gave mixtures of higher modulus and lower extrusion shrinkage. Although it was possible to measure the carbon black structure directly, it was also shown to be good. and a more convenient method of determining the carbon black structure is to measure the oil adsorption by the carbon black. It is the kind of oil adsorption measurement technique to determine the structure of carbon black which was adopted and designated as ASTM Test Method D-2414-72, entitled "Dibutyl Phthalate Absorption Number of Carbon Black". by adding in a Brabender - Cabot Absorptometer by CW Braben der Instruments, Inc., South Hackensack, NJ to a sample of granular or powdered butyl phthalate and measuring the volume of phthalate consumed. This value is expressed in cm5 or milliliters of phthalate. butyl (DBP) per 100 grams of carbon black. In the process of the present invention, the raw material from which the carbon black is formed is injected substantially transversely into the previously produced flue gas stream flowing in the downstream direction at an average linear velocity of up to at least 30.48 m / sec, and preferably at least 152.4 m / sec. The raw material is injected into the flue gases transversely to their flow direction and on the circumference of their stream in such an amount as to achieve penetration and to avoid the formation of coke on the walls of the reactor in the soot zone. A novel feature of the process according to the invention is the introduction into the primary reaction zone of the exemplary carbon black process, a certain amount of auxiliary heat or gaseous hydrocarbon. As stated previously, the primary reaction zone is downstream of the injection point of the hydrocarbon from which the soot is formed in the flow direction, that is to say between 2 and 60 thousand distances from the point of injection of the hydrogen carbon from which the soot is formed to the point of injection. cooling medium. As a result of the addition of the auxiliary hydrocarbon, the carbon blacks produced showed a much higher structure as evidenced by an increase in the adsorption of butyl phthalate by at least 5 ml per 100 g of carbon black. Moreover, if the carbon blacks obtained by the process of the invention are incorporated into rubber mixtures, the physical properties of these mixtures are improved. The carbon black production process according to the invention is carried out as follows. In order to obtain the hot flue gases used for the production of high carbon black the structure of a suitable combustion chamber, the liquid or gaseous fuel is reacted with a stream of a suitable oxidant, such as air, oxygen, oxide-air mixtures, etc., for fuels suitable for use in reaction with an oxidant stream in any flammable gas, vapor or liquid such as hydrogen, carbon monoxide, methane, acetylene, alcohols, kerosene can be used in the combustion chamber to produce hot exhaust gases. In general, however, it is preferable to use fuels with a high proportion of carbonaceous constituents, in particular hydrocarbons. For example, methane-rich gases such as natural gas and modified or enriched natural gas are excellent fuels, as are other hydrocarbon-rich fuels such as various gaseous and liquid hydrocarbons and refinery byproducts. such as ethane, propane, butane and pentane fractions, fuel oils, and the like. Preferably, air is used as the oxidant in the first step of the reference kiln process and natural gas as the fuel to form the primary combustion flame. Primary combustion here means the amount of air in the first step of the reference process relative to the amount of air required to completely burn the hydrocarbon in the first step. For convenience, primary combustion is expressed as a percentage. Although it may vary in the range 100-250%, the primary combustion in the first stage is preferably 120-150%. In this way a hot flue gas stream is produced which flows at a high linear velocity. It has further been found that the pressure difference between the combustion chamber and reaction chamber is at least 0.07 kg / cm 2, and preferably 0.106-0.7 kg / cm 2. Under these conditions, a stream of gaseous combustion products is formed with an energy sufficient to convert the carbon-hydrocarbon raw material from which soot is formed into the desired product. The resulting flue gas coming out of the combustion stage has a temperature of at least 1300 ° C and preferably greater than 1635 ° C. The hot exhaust gas rushes in the direction of flow at a high linear velocity, increased by introducing them into a closed transition stage of a smaller diameter, which can be narrowed or reduced if necessary, for example, a Venturi tube. It is at this point in the process that can be regarded as the second stage and where raw material is rapidly injected into the flue gas stream. More specifically, the second stage where the flue gas flows at a high speed and where there is a dynamic impulse. gas is at least greater than 0.07 kg / cm 2, a suitable hydrocarbon is injected into the flue gas at a pressure sufficient to achieve the desired penetration, thus ensuring a high mixing and shearing speed of the hot gases gas and hydrocarbon feed. As a result of the prevailing conditions, the hydrocarbon feedstock rapidly decomposes and is converted to carbon black with high efficiency. Those hydrocarbon feedstocks which are volatile under the reaction conditions are suitable for use in the process of the invention. These include unsaturated hydrocarbons such as acetylene, olefins such as ethylene, propylene, butylene, aromatic hydrocarbons such as benzene, toluene, and xylene, certain saturated and vaporized hydrocarbons such as kerosene, naphthalenes, terpenes, ethylene tars, aromatic hydrocarbons, etc. The feed is injected substantially in a transverse direction from the periphery of the hot flue gas stream as small coherence jets that penetrate well into the interior regions of the flue gas stream, but not In the practice of the invention, the hydrocarbon feed is injected as a liquid stream by forcing the liquid raw material through multiple holes with a diameter of 0.254-3.8 mm, preferably 0.508-1.524 mm in diameter. mm at a pressure sufficient to achieve the desired penetration. The amount of the raw material is selected depending on the fuel and oxidant used, so as to achieve a total combustion of 15-60%, preferably 20-50%, for the soot production process. Total combustion means the total amount of air used in the process. soot formation relative to the amount of air required for complete combustion of all the hydrocarbon used to carbon dioxide and water. They are usually expressed as a percentage. The third step of the reference process is carried out in a reaction zone which provides a residence time for the reactants sufficient for the soot reaction to take place before the reaction is terminated by cooling. Typically, although the residence time in each case depends on the particular conditions and the type of carbon black desired, it will be from 1 millisecond or less to over 100 milliseconds in the present invention. Accordingly, when the sooting reaction has run for the desired period of time, it is interrupted by spraying a cooling liquid, such as water, using at least one set of nozzles. Hot exhaust gases containing the carbon black product suspended therein then flowing in the flow direction to the known stage of cooling, separating and collecting black. The separation of the soot from the gas stream is readily accomplished in known devices such as. electrostatic precipitators, cyclones, bag filters or combinations thereof. It has been found that the structure of the soot produced by the benchmark process described previously can be greatly enlarged to suit applications requiring high soot structure. The structure of the carbon black is increased, in particular, by introducing a certain amount of gaseous or liquid hydrocarbon, hereinafter referred to as auxiliary hydrocarbon, in the predetermined primary reaction zone in the predetermined reaction zone. The individual hydrocarbons used as auxiliary hydrocarbons need not be the same as the original hydrocarbon feed. Usually, the introduction of the auxiliary hydrocarbon in gaseous or liquid form into the reference process causes an increase in the structure of the soot, which gives the rubber mixtures containing it a higher modulus. The amount of auxiliary hydrocarbon used in the method according to the invention, or in the liquid phase or gaseous, is defined as a percentage of the total amount of carbon (C) in the reactants introduced into the process. In particular, the amount of auxiliary hydrocarbon used is determined by the following equation:% C in auxiliary hydrocarbon = total amount of carbon in kg in reagents X100. kg of carbon in the auxiliary hydrocarbon • In this equation, the total amount of carbon introduced as reactants is the amount of carbon introduced in the reactants for the first stage, the amount of carbon introduced in the hydrocarbon feedstock from which soot is formed, and the amount of carbon introduced into the form of a hydrocarbon auxiliary Typically, the auxiliary hydrocarbon is used in an amount of 2 to 60% by weight of the total amount of carbon contained in the reactants. When a liquid auxiliary hydrocarbon is used, its amount is preferably such that the amount of carbon in this hydrocarbon is 5-60%, especially 10-15%, based on the total amount of carbon incorporated in the reactants. On the other hand, when hydrocarbon gas is used as auxiliary hydrocarbon, its amount is 2-10% by weight of the total amount of carbon introduced into the system, and preferably 4-8%. For the evaluation of the analytical and physical properties of the carbon black produced according to For the invention, the following procedure is used. Iodine adsorption value - is determined in accordance with ASTM D-1510-70. The specific surface area is determined by the iodine adsorption method. The specific surface area of granular carbon black product is determined by the following iodine adsorption method. The soot sample is placed in a porcelain crucible with a loosely fitting cover to allow the gases to escape, and is volatilized by heating for 7 minutes in a muffle furnace at 926.6 ° C and then allowed to cool. The top, baked layer of soot on the soil and a bone of 6.35 mm is removed and the remainder is weighed. 100 ml of 0.01 N iodine solution are added to this sample and the resulting mixture is stirred for 30 minutes. An aliquot of 50 ml of the mixture is centrifuged until a clear solution is obtained, then 40 ml of this solution is titrated in 0.01 N sodium thiosulfate solution in the presence of a 1% starch solution as an indicator of the end of the titration, until free iodine is adsorbed. The percentage of iodine adsorbed is quantified by titration of the blank. The specific surface area determined by the iodine adsorption method and expressed in m2 / g is calculated according to the formula: ii Area / Absorbed percentage of specific iodine X0.937 / -45 _ determined Sample weight iodine adsorption method io This method of determining the surface area of granular carbon black is determined for convenience, as Cabot Test Procedure No 23.1 as it is still not marked by ASTM. As reported in Cabot Corporation publication TC-70-1, entitled "Insdustry Reference Black No. 3", issued by Messrs. Juengel and O'Brien on April 1, 1970, IRB carbon black surface area No. 3, (Industry Reference Black No. 3) means M iodine adsorption method is 66.5 m 3 / g. Bulk density of granular carbon black - is determined according to ASTM D-151 and is expressed in pounds (cubic feet / kg). The number of absorption by the butyl phthalate carbon black is determined according to ASTM Test Method D-2414-72 as previously described. The reported results indicate whether the carbon black was tested in granular or dusty form. Dyeing strength. Coloring strength. It has a hiding ability of granular carbon black incorporated 37.5 parts by weight into the standard zinc oxide (Florence Green Seal No. 8, manufactured and sold by New Jersey Zinc Co.) dispersed in an epoxidized soybean oil type 45 plasticizer. / Paraplex G-62 manufactured and sold by Rohm and Haas C. compared to a series of standard carbon blacks tested under the same conditions. More specifically, this test consists of grinding the carbon black, zinc oxide and plasticizer in such proportions that the resulting ratio of carbon black to zinc oxide is 1: 37.5 . The Welch Densichron apparatus measures the light reflectance of the film cast on a glass plate from the mixture obtained by comparing the readings with samples containing standard blackberries of known tinting strength. The tinting strength of standard carbon blacks is determined by the tinting strength of 60 Cabot's standard SRF carbon black, assumed to be 100%. This standard carbon black with 100% tinting strength is furnace semi-strengthening carbon blacks with the trade names Sterling S or Sterling R manufactured by Cabot Corporation. Each of these comparative carbon blacks, 85 Sterling S or Sterling R, has the following properties, among others: specific surface area determined by BET / nitrogen absorption method / 23 m2 / g, oil absorption 65-70 kg oil / kg are Between and the average particle size as determined by an 800 A electron microscope. The only difference is that the Sterling R carbon black is dusty, while the Sterling S carbon black is granular. Accordingly, a standard judgment is selected against which the determination is made. Thus, sterling R or Sterling S semi-reinforcing carbon blacks have been found to be excellent references to determine the tinting strength of other carbon blacks. In addition, as stated previously, to determine tinting strengths of 30-250%, other judges are also used as comparative . Their tinting strength was initially determined in relation to the standard carbon black, the tinting strength of which was assumed to be 100%. In this way, he obtains a number of carbon blacks over a wide range of dyeing strengths so as to provide a comparative carbon black with the tinting strength as close as possible to the dyeing strength of the carbon black being tested. the names and properties marked are summarized in Table 1. For comparison, labeled as described previously in Cabot Corporation ^ Technical Service Report No. TG-67-1 titled "The Use of Multi Section Treads in Tire Testing "edited by Fred Jones (1967). It should be noted that for any method of measuring the wear rate, the evaluation is made against a standard comparative carbon black which has been set at 100% wear rate in advance. In this case, the comparative standard is the reference standard. ISAF carbon black / internmediata super abrasion furnace was selected to assess road wear - furnace soot with medium abrasion resistance / marked according to ASTM with the symbol N-220, manufactured by the Cabot Corporation, with the following properties: tinting strength 232%, specific surface determined by iodine adsorption method 97.9 m2 / g, butyl phthalate adsorption / DBP / 114.9 cmS / 100 g, density 0.3592 g / cm8. For ease of use, this tire tread wear comparative carbon black is described as ISAF comparative carbon black No. D-6607 manufactured by Cabot. The above method for determining the relative wear rate of tread compounds is preferred when used in laboratory tests. abrasion resistance measurement because it is known that it is difficult to trap such results into actual road behavior. The results of the road wear tests given here reflect exactly the table 1 Analytical properties Dyeing strength,% Specific surface area determined by the method of iodine adsorption m2 / g Adsorption of butyl phthalate cm8 / 100 g iSterling MT / Medium Thermal - thermal average 31 5.0 & 3 , 6 Sterling PT / Fine Thermal - fine thermal l56 8.4 35.9 yulcan 1 6H £ 20 110, 131 yulcan 9, 252 119 117 tinting power of IRB No 3 carbon black compared to standard Sterling S semi-reinforcing carbon black is 208%. This is stated in the aforementioned Cabot Corporation publication, TG-70-1, Industry Reference Black No 3, published by Messrs. Juengel and O'Brien, April 1, 1970. Modulus and Strength. Physical properties are determined by ASTM Test Method D-412 Briefly, the measurement of the module relates to the load in kg / cm 2 observed when the vulcanized rubber sample is stretched to 300% of its original length. The strength is the load in kg / cm 2 required to break. or cracking of a vulcanized rubber sample in a strength test. Road friction rate. The method of measuring and evaluating the road wear or wear of a tire is known in the art and the overall behavior of tread compounds compared to standard soot ISAP No. D-6607, manufactured by Cabot with a pre-imposed value of 100%. To carry out the previously given road wear assessments, a rubber compound is used with the following composition: expressed in weight parts, which is formulated in Banbury mixer: Ingredient Weight parts Styrene butadiene rubber 89.38 Cis-4-polybutadiene rubber 35 Carbon black 75 Sundex 790 25.62 Zinc oxide 3 Sunproof Improved 2.5 Wingstay100 2 Stearic acid 2108 421 U Santocure / CBS / 1.4 Sulfur 1.75 In the above mixture, intended for road tests, marked with the symbol RTF-1, Santocure (CBS) means the trade name of the vulcanising agent in rubber mixtures - N-cyclohexylbenzothiazole-2 sulfonamide, Sundex 790 is the trade name of the plasticizer introduced marketed by the Sun Oil Company, Sunproof Improved is the trade name for the anti-ozonant marketed by Uniroyal Chemical Company and Wingstay 100 is the trade name for the mixed diaryl-p-phenylenediamine stabilizer marketed by Goodyear Tire and Rubber Company. The method according to the invention is more fully explained in the working examples which describe the specific production of representative products. These examples are given for the purpose of illustration only and do not limit the scope of the invention. Example I. A suitable reaction apparatus is used, equipped with a device for feeding with reactants that produce flue gas, i.e. fuel and oxidant stream, either as separate streams or in the form of pre-burned gaseous reaction products, as well as a device for supplying the apparatus with both a hydrocarbon feed from which the soot is formed and a secondary hydrocarbon feed. The apparatus may be made of any suitable material, such as metal, and provided with flame retardant insulation, or surrounded by a cooling device for a circulating liquid which is preferably water. In addition, the reaction apparatus is equipped with a temperature and pressure recorder, soot cooling devices such as spray nozzles, devices for cooling the soot produced, and devices for separating and recovering soot from other undesirable by-products. The following procedure is used in the production of high-structure carbon black according to the invention. The combustion zone of the apparatus is charged through one or more inlets with air preheated to a temperature of 398 in order to obtain an excess flame in the first stage. 8 ° C in the amount of 2.405 · 10 * hr and natural gas in the amount of 172.3 m3 / hour, resulting in a stream of exhaust gas flowing downwards at a high linear speed, having a dynamic pressure of at least 0.07 kg / cm2. In this case the percentage of pre-combustion or first stage combustion is 14.7%. The fast flowing stream of exhaust gas flows into a second or transitional stage with a smaller diameter in cross section to increase its linear velocity. Then into the resulting stream of hot exhaust gas with the desired dynamic pressure substantially in the transverse direction through four inlets arranged around the circle. of this stream, each 0.914 mm in size, a carbon black feed of 612.92 liters / hour is introduced at a pressure of 17.74 kg / cm2. The hydrocarbon feedstock is Shamrock thermal tar, which is a fuel with a carbon content of 91.4 wt%, a hydrogen content of 8.37 wt%, a sulfur content of 0.48 wt%, a hydrogen to carbon ratio of 1.09. correlation index according to BMCI 118, specific weight according to ASTM D-287 1.07, API specific weight according to ASTM D 287+ + 1.2, viscosity SSU / According to ASTM D-88 / at a temperature of 54.4 ° C of 53 9, the SSU viscosity (according to ASTM D-88) at 98.9 ° C was 0.06 and the asphaltene content was 5.7%. The reaction is carried out with a total combustion of 31.9% and water cooling with a cooling device placed at a point 3.81 m from the original injection point in the flow direction. Carbon blacks with an iodine adsorption number of 90, a specific surface area determined by the iodine adsorption method of 70 m2 / g, a color value of 229 * / *, an adsorption value of butyl phthalate by carbon black in a dusted state of 149, an absorption value of butyl phthalate by granulated carbon black 124, pH value 9.5, gross weight 32 kg / m *. This carbon black was used as a control sample, in the preparation of which no auxiliary hydrocarbon was added. Example II. Proceeding as in Example I, the combustion zone is fed with air of 2.405 · 10 * ma / hr preheated to 398.8 ° C and natural gas of 171 m · 2 / hr, achieving the desired conditions in the first stage of combustion. Combustion in the first stage is 14.7%. The flue gas then passes to a second stage with a smaller diameter in cross-section, where the primary hydrocarbon feedstock, Sham-rock thermal tar, 629.27 liters / hour under pressure, is injected through 4 holes, each 0.916 mm in diameter. 16.2 kg / cm2. At a point 0.914 m downstream of the primary injection point of the hydrocarbon feed and in the primary reaction zone described here, the Shamrock thermal tar 98.59 liters / hour is introduced as auxiliary hydrocarbon. It is introduced through the side wall of the reactor into the flue gas contained therein by means of a ring-shaped, water-cooled test sample equipped with a 60 ° Monarch spray tip with an opening diameter of 0.458 mm. The reaction is carried out with a total percent burn of 30.8% and is cooled with water at a point 4.115 meters downstream of the injection point. Carbon black is obtained which, when analyzed, show properties in all respects similar to the control sample obtained in Example 1, except for a much taller structure, as evidenced by a 17 point increase in the adsorption value of butyl phthalate to granulated carbon black. The amount of the auxiliary hydrocarbon used in this example, calculated as previously stated, is such that the carbon content of the auxiliary hydrocarbon is 11.6% by weight 10 15 20 25 30 35 40 45 50 55 60 108 421 13 based on the total carbon content of the reactants. Example III According to the procedure described in Example 2, the air preheated to 398.8 "C in the amount of 2.0405 • 108 m8 / hour is combined with natural gas at 172.1 m8 / hour to ensure the first stage Combustion 147% The hot exhaust gas flows to a second or transitional stage in which, through four 0.916 mm diameter holes, the primary hydrocarbon feed, i.e. the Shamrock thermal tar, 642.90 liters / hour, is rapidly introduced into the flue gas stream. at a pressure of 21.1 kg / cm.sup.2 In this case, at a point 1.219 m downstream of the injection site using a water-cooled sampler and sprayer as described in Example II is injected as an auxiliary carbon. Shamrock thermal tar at 98.59 liters / hour This amount of auxiliary hydrocarbon is chosen such that it has a carbon content of 11.6% by weight, based on the total carbon content of the reactants. The conditions are such as to obtain a total combustion of 30.6%, and the cooling is carried out at a point 5.638 m away from the point of injection of the original hydrocarbon feed. Carbon blacks are obtained with similar properties to the control sample prepared in Example I, such as the surface area determined by the iodine adsorption method of 71 m2 / g, a color value of 233%. and pH 8.6. However, as in Example 2, the carbon black produced has a much higher structure, which indicates an increase of 14 points in the adsorption value of butyl phthalate by both granulated carbon black and dusty carbon black. Examples 4 through 7 demonstrate a process for the production of carbon black of the type prepared in Example 1, in which the combustion in the first stage was reduced to 126%. and according to the method of the invention, in order to increase the level of the carbon black structure, an auxiliary injection of the hydrocarbon feed is used, in particular, into the combustion zone, proceeding as in Example II, air preheated to a temperature of 398.8 ° C is introduced. C in the amount of 2.405 • 108 m3 / hour and natural gas in the amount of 200 m3 / hour so as to provide the desired flame of which the primary combustion is 126%, the resulting hot gaseous products of combustion flow to the second or intermediate stage where The flue gas is fed as a primary feedstock hydrocarbon oil, namely Shamrock thermal tar. More specifically, the original hydrocarbon feed is introduced at a rate of 630.64 liters / hour through four openings, each 0.916 mm in diameter, at a pressure of 15.5 kg / cm 2. At a point 0.914 m downstream from the oil injection point, you additionally add Shamrock thermal tar in the amount of 98.59 liters / hour, which corresponds to the amount of hydrogen carbon with a content of 11.5% by weight of carbon based on the total content. carbon in 14 agents. The sooting reactions are carried out with a total combustion of 30.1% and completion by cooling at a distance of 4.114 m downstream from the injection point of the original oil. In this way, carbon blacks are produced which, on analysis, exhibit similar properties to the control sample prepared in Example 1, with a specific surface area determined by the iodine adsorption method of 69 m2 / g, a color of 235%, and a pH of 8.8. However, as in Examples I and II, the injection of auxiliary liquid hydrocarbon at a specific amount and distance increases the value of the butyl phthalate adsorption index by 28 points, indicating a higher structure of the soot obtained. in Example IV, a first step produces flue gas by burning 2.405.10 m8 / hr of air preheated to 398.8 ° C and 200.4 m8 / hr of natural gas to provide primary combustion 126%. The hot gases formed in the first stage flow in the flow direction to a transition stage where 627 liters / hour of the original hydrocarbon feed is injected rapidly into the periphery of the exhaust gas stream. Shamrock thermal tar is used as the primary hydrocarbon feed and is injected into the gas stream through four openings of 0.916 mm diameter at a pressure of 15.5 kg / cm2. In this case, the auxiliary amount of Shamrock thermal tar is introduced in the same amount as in Example IV, ie 98.59 liters / hour, corresponding to a carbon content of 11.5%. by weight of total carbon content of the reactants. The secondary hydrocarbon is introduced 1.219 m downstream of the injection site of the primary hydrocarbon feed, and not 0.914 m as in the preceding example. The reaction conditions are maintained such that total combustion in the carbon black process is 30.2% and cooling is from a point 5,638 meters downstream from the injection site of the hydrocarbon primary feed. 45 carbon blacks were obtained, showing properties similar in all respects to the control sample prepared in Example 1, except for the desired higher level of structure, as a result of an increase in adsorption of butyl phthalate by 50 granulated carbon black by 30 points and carbon black in dusty state by 26 points. As for the other properties to be determined, the resulting carbon black surface has a suitable surface area determined by the iodine adsorption method of 70 m2 / g, a coloration of 239% and a pH of 8.8. 55 Example VI. The procedure of Example 5 is followed with the following exceptions: The primary raw material is introduced in an amount of 613.3 l / hour which slightly increases the amount of auxiliary hydrogen added so that the carbon content is 11.7% and not 11.5 wt.% based on the total carbon content of the reactants. - Other changes are that the raw material is injected under a pressure of 26 kg / cm 2 and the total combustion is 30.7%. The greatest difference is that the auxiliary hydrocarbon is introduced at a distance of 1.524 m from the injection point of the primary hydrocarbon feed in the direction of the stream flow. As a result of these modifications, carbon blacks are obtained with analytical properties almost the same as for the example IV carbon blacks, but with a much higher structure. However, the adsorption value of butyl phthalate (DBP) by the granular carbon black obtained in this example is 139, i.e. 15 points more than that of the control sample of Example I. The analytical properties of the carbon black were then appropriately measured. method of iodine absorption 69 m * / g, color 235 ° / * and pH 8.9. Example VII. The procedure is essentially as described in Example V. However, the raw material is introduced at a rate of 610.64 liters / hour at a pressure of 17.9 kg / cm 2. The most important change consists in introducing a hydrocarbon aid in the amount of 111.3 liters / hour. so that the carbon content of the auxiliary hydrocarbon is 13.1% by weight, based on the total carbon content of the reactants. The introduction of the auxiliary hydrocarbon occurs, as in Example V, at a point 1.219 m from the injection point of the primary feedstock in the flow direction. The obtained carbon black has a surface with a suitable iodine adsorption method of 70 m / g, a color of 239%, a pH of 8.7 and a value of butyl phthalate absorption by granulated carbon black of 157. It is evident that the carbon black of this example has a much higher structure. Than the control sample, the adsorption value of butyl phthalate is only 3 points more than that of the soot of Example V. Increasing the amount of auxiliary hydrocarbon introduced caused the structure to grow only slightly. The abrasion rate on the road for the soot obtained is 101%. For ease of use, the data from Examples 1-7 are shown in Table 2. This table also illustrates the properties of the carbon black rubber, with both synthetic rubber mixtures (ISR) and mixtures with Natural rubber (NR). The use of the carbon black obtained according to the invention as a reinforcing agent in rubber mixtures is illustrated by the following examples. The rubber mixtures are easy to hold by known methods. For example, the rubber is thoroughly blended with carbon black as a reinforcing agent in a mixer commonly used to mix rubber or plastics such as a Banbury mixer and / or a rolling mill to obtain adequate dispersion. The rubber compounds are of the same composition as standard industrial compounds for both synthetic and natural rubber compounds. The obtained vulcanizates are vulcanized at a temperature of 144 ° C for 30 minutes when using natural rubber and for 50 minutes when using styrene-butadiene synthetic rubber. The following mixtures are used to evaluate the effect of the carbon black according to the invention. are given in parts by weight. Component Composition of the mixture Composition of the mixture 5 of natural synthetic rubber Polymer 100 / caoutchouc 100 / natural rubber / styrene-butadiene rubber / 10 Zinc oxide 5 5 Sulfur 2.5 2.0 Stearic acid 3 1, 5 Altax (MBTS) 0.6 2.0 Carbon black 50 50 15 Altax (MBTS) is the trade name for mercaptobenzothiazole disulfide accelerator used by RT Vanderbilt Company. Table 2 shows the unexpected results obtained by using carbon black prepared in accordance with the invention. as an additive to rubber mixtures. From the above data it follows that the carbon black structure can be significantly increased by introducing auxiliary equipment. In this case, the auxiliary hydrocarbon is introduced in a liquid state and the injection is controlled both in terms of quantity and location. At the same time, in addition to an increase of 14-33 points of DBP adsorption by the granulated carbon black, the modified carbon black obtained in this series of experiments causes a significant increase in the modulus of natural rubber mixtures. In the case of synthetic rubber mixtures, the lower value of shrinkage after extrusion indicates the use of carbon black with a higher structure. The increase in structure is not accompanied by a negative effect on the economics of the carbon black production process, such as a reduction in processing and / or efficiency. Example VIII. Examples VIII, IX and X show an increase in the carbon black structure by using a greater amount of auxiliary hydrocarbon. In this example, a carbon black control sample having a surface area determined by iodine adsorption method 72.4 m2 / g, color 230%, DBP adsorption value 135 is prepared by the method of example 1. In the first step of the carbon black production process, the combustion is 112 %, which is achieved by introducing 2.405 · 10 * m8 / h of air pre-heated to 398.8 ° C and 234 ms / h of natural gas. 640.6 l / h of hydrocarbon feedstock is injected into the flue gas stream with great force at a pressure of 21.9 kg / cm2 through 8 holes each with a diameter of 0.762 mm. The hydrocarbon material used in Examples VIII-X is a Sunray DX fuel containing 91.1%. carbon, 7.9 wt.% hydrogen, 1.3 wt.% sulfur, in which the ratio of hydrogen to carbon is 1.04, the lerance index per gram of BMCI 133 specific gravity according to ASTMD-287 is 1.09. Specific gravity in ° API according to ASTMD-287 is - 2.6, viscosity of SSU (according to AST M D-88) at 54.4 ° C is 350, viscosity of SSU (according to ASPM D-88) at mp 98 , 9 ° C is 58 and the bitumen content is 17 108 421 18 Table 2 Analytical properties of carbon black Sample 1 of carbon black I Iodine adsorption value Example I 1 90 Example II Example III Example IV Example V Example VI Example VII 90 89 84 90 87 90 1 Physical properties \ Soot test 1 Strength kg / cml in / g ASTM J D-412 / I Modul 300%, 1 kg / cm * in / g ASTM 1 D-412 / Specific surface marked with iodine adsorption m «/ g 70 72 71 69 70 69, 70 mixes Example I —14.7 +26 Color strength ¦ / • and SRF 229 235 233 235 239 235 PH 9.5 8.7 8 , 6 8.8 8.8 8.9 239 8.7 1 1 1 Adsorption of DBP by granulated carbon black m8 / 100 g 1 Total weight kg / cm * 1 124 141 138 152 154 139 157 325.26 307.58 309.18 209.56 301.17 318.79 297.9 1 natural and synthetic rubber h Example II Example 1 m Example 1 IV Natural rubber mixture f. - 8.4 ¦ + 44.2 - 9 . 1 1 + 39.3 [^ 14 +44.9 | Carbon content in coal-1 auxiliary water% '- '11.6 1 11.5 11.5 11.7 13.1: rubber * Example V sm / 1— 7.7 +42.8 Distance j from points of auxiliary hydrocarbon injection 1 to the point of primary raw material injection m - 0.914 1.219 0.914 1.219! 1.524 '1.219' Example VI W- 6.3 | +42.1 "and 'DBP adsorption by and dust soot ¦cmV 100 g 149 '160 163 165 .175' 155 177 Example | VII f% \ ^ -8.4 +53.4 | 1 Synthetic rubber compound / ISR / J 1 Strength, kg / cm8 w / g ASTM 1 D-412/1 Plasticity according to Mooney Shrinkage after extrusion, • / • IRB No. 3 1 + 25.3 + 6 93.6 | + 18.9 1 + 11 1 '87.1 |' + 3.5 1+ 8 87.3 | + 16.1 1 1 + 10 | '85.2 | lW' +11 84.5 | (- 4.9 1 y + 7; 87.8 1 (+ 0.7 '+1 »2 | i lv 83.8 1 * All physical properties are expressed in terms of carbon black type JRB No. 3 / Industry Reference Black No. 31 / ten 5,7% Reactions are carried out at full VIII the primary lys combustion is obtained * / * At this combustion of 28.9% and cooling down to the gas stream The crude oil is injected at a point 3.2 m from the hydrocarbon injection point, which is Sunray oil of the hydrocarbon feed in the DX direction at a rate of 481.6 l / hour at a pressure of 15.4 jet flow. kg / cm2. The hydrocarbon feed is introduced in Example IX. Following Example C5 through 8 holes each 0.762 mm in diameter 108 421 19 Hydrocarbon auxiliary oil Sunray DX is introduced into the flue gas stream at a distance of 1.219 m from the entry point of the primary feed at 113.58 liters / hour. The reaction conditions are maintained so as to obtain a total combustion of 30.5%. Cooling takes place at a distance of 5.638 m from the injection point of the primary raw material. The soot produced with the carbon content in the auxiliary hydrocarbon of 15.2% by weight in relation to the total carbon content in the reactants has a proper surface determined by the method of iodine adsorption 74.2 m / g, color 230%, and DBP adsorption value by granulated carbon black 169, which indicates an increase in its structure by 34 points compared to the carbon black from Example VIII. Example X. Primary combustion of 112% is obtained in as in Example VIII. Then, as in Examples VIII and IX, Sunray DX is injected through 8 holes each with a diameter of 0.762 mm as a hydrocarbon feedstock at 449.8 liters / hour at a pressure of 13.3 kg. / cm *. At a distance of 1.828 m from the feed point, an additional amount of Sunray DX hydrocarbon at 113.58 liters / hour is injected in the direction of the flow so that the B carbon content of the auxiliary hydrocarbon is 15.9% by weight based on the total amount. carbon in reagents. Reactions are carried out with a total combustion of 31.8%, and cooling is effected 5.638 meters from the point of injection of the original feedstock, downstream. The produced carbon black has a surface with a suitable iodine adsorption method of 73.7 m2 / g, a coloration of 228% and a DBP adsorption value by granular carbon black 169. This example shows that an additional distance from the injection site of the primary raw material to the site the addition of auxiliary hydrogen does not result in a further increase in the structure of the soot than that obtained in Example IX.M. The data of Examples VIII, IX and X and the properties of the rubber compounds are presented in Table 3. Examples XI and XII are presented in Table 3 Analytical and physical properties of carbon black Sample of carbon black Specific surface area determined by iodine adsorption method m * / g | Iodine adsorption value ma / g Dyeing power% SRF DBP adsorption by granular carbon black cm »/ 100 g DBP adsorption by powdery carbon black cmtyl 100 g Density kg / m8. Carbon content in auxiliary hydrocarbon% 'Distance from the primary raw material injection point to the hydrocarbon injection point auxiliary m Example VII | 72.4 | 89 | 230 135 168 323.6. Example IX 1 74.2 89 330 169 200 301.17; 15.2 1.219 Example X 1 73.0 [86 [f - 228 f 169 1 '205 f' 291.5 f 15.9 '. 1 1,828 [Natural rubber mixture, / NR / * fj Strength kg / cm * | / w / g HSTM D-112 J Modul, kg; / cm * / w / g ASTM D-412 / - '2.9 + 33 - 7.7 +48.5 —14.7 | v + 46.3 \ Synthetic rubber mixture / ISR / * 'Strength kg / cm * / ASTM D-412/1 Modul kg / cm2 / ASTM D-412/1 Plasticity according to Mooney / ASTM D-1646 / 1 Shrinkage after extrusion% IRB No. 3 + 3.5 | + 39.3 1 + 8 1 93.1 | + 5.6 | + 56.2 | + 13 | '82.6 | - W | +52 r + 11 f '83.2 | * all the physical properties of the mixtures are expressed with respect to carbon black type IRB No. 3.108 421 21 22 which is a preferred embodiment of the method according to the invention. These examples clearly show that the carbon black structure increases as a result of the injection of the auxiliary hydrocarbon at the same points as the hydrocarbon feedstock is injected. This is explained by the following detailed process data. In a suitable reaction apparatus, 11.91 mV / h of air, preheated to 382 ° C., is combined with 1.047 m 3 of natural gas in a first stage to obtain hot exhaust gas. The gas stream flows downwardly into the transition zone where, through 11 holes with a diameter of 1.27 mm, 2080.9 l / h of primary hydrocarbon feed is injected into the stream at a pressure of 18.77 kg / cm *. At the same point where the hydrocarbon feed is injected, an additional amount of 826.9 liters / hour of the same oil as the feed oil is introduced with a water-cooled sampler axially in the direction of flow. The hydrocarbon feed used is Clark decanted oil, which is a fuel having 90.99% by weight of carbon, 8.04% by weight of hydrogen and 1.3% by weight of sulfur, the hydrogen to carbon ratio being 1. , 05, correlation index according to BMCI 121, specific gravity according to ASTM D-287 is 1.07, specific gravity in ° API according to ASTM 0-287 is 0.9, viscosity SSU / according to ASTM D-88 / w at 54.4 ° C is 150.8, the viscosity of SSU (according to ASTM D-88) at 98.9 ° C is 44.7 and the asphaltene content is 2.19 / *. The reaction conditions are maintained such that a total combustion of 319% is achieved and the cooling is done at a distance of 3.352 meters from the point of injection of the feed in the flow direction. As a result of the use of auxiliary hydrocarbon, a carbon black with a good iodine adsorption value of 9 * 2, a specific surface marked by the iodine adsorption method 74 m2 / g, a coloration of 237%, a bulk density of 297.9 kg / m3, is obtained, adsorption of DBP by granular carbon black 155 cm * / / 100 g, which is 25 points higher than the control sample of Example XII. Natural rubber mixtures are characterized by the following physical properties - module 300 * / t + 38.6 kg / cmf, strength - 9.13 kg / cm *, for synthetic rubber mixtures module 3009 / * it is +70, 3 kg / cm *, strength +48.5 kg / cm *, and shrinkage after extrusion 84.19%, the physical properties of the mixtures were determined in relation to carbon black type IRB No. 3. The road wear rate for the obtained carbon black is 1049 /*. Example XII. The procedure is as in example XI. The air, preheated to the temperature of 436.6 ° C, in the amount of 1 (2.73 × 109 mV / h) is combined with natural gas in the amount of 1.018 × 10 m / h, reaching the primary combustion of 1259 / *. Hot flue gases liquid downwardly to a transition stage in which a feed oil of 2,916.9 liters / hour is strongly injected into the gas stream through 9 holes, each with a diameter of 1.524 mm, at a pressure of 21.09 kg / cm 1. These reaction conditions are maintained. In order to obtain a total combustion of 339 µm, the cooling to 676.6 ° C is carried out at a point 2.133 m from the point of injection of the oil feed in the direction of the flow. The result is a carbon black with an iodine adsorption value of 90, a ratio of 320, 4 kg / m3, the specific surface area determined by the iodine adsorption method 71 m2 / g, color 235% and DBP adsorption by granulated carbon black 130. Natural rubber mixtures containing these carbon blacks have a modulus of 3009 / vol. + 29.5 kg / cmf strength essentially the same as for control carbon black type IRB No. 3 The synthetic rubber containing the carbon black prepared in this example has a modulus of 300% + 56.2 kg / cm2, a strength of +56.24 kg / cm2 and a plasticity of Mooney +8. The value is compared to the control carbon black type IRB No. 3. The road wear rate is 100 ° C. Example XIII. In Examples 13 to 15, natural gas is used as an auxiliary hydrocarbon. These examples are intended to illustrate the effect of varying the location of the auxiliary gas injection while keeping the amount approximately constant. The carbon black of Example 1 is used as a control sample. Following the procedure described in Example 1, an initial combustion of 140% / t is obtained by combining 2.405 · 109 m / hr of air preheated to 398.8 ° C with 0 ° C. , 1723 • 10 * m9 / hour of natural gas. The hot flue gas is fed stepwise through 4 holes, each 1.01 mm in diameter, into a hydrocarbon feed of 562.48 liters / hour at a pressure of 14.48 kg / cmf. As a raw material, Shamrock tar with a carbon content of 90.7% by weight, a hydrogen content of 8.359% by weight, a sulfur content of 0.59% by weight of a hydrogen to carbon ratio of 1.09, a correlation coefficient w / g BMCI 118, specific gravity according to ASTMD-287 being 1.06, specific gravity in API according to ASTM D-287 being 2.0, viscosity SSU (according to ASTM D-88) at 54.4 ° C being 252 , the viscosity of SSU (according to ASTM D-88) at 98.9 ° C, 53.8, and an asphaltene content of 5, T / *. Natural gas is then injected into the flue gas stream in an amount of 0.068.10 mV / h, which gives a carbon content of the auxiliary gas of 6.2% by weight, based on the total carbon content of the reactants. The auxiliary gas is introduced at a distance of 0.609 m downstream of the feedstock injection point in the flow director by suitable devices, for example a water-cooled pipe having a diameter of 1.27 cm and having a Monarch spray tip 0.86 cm in diameter. The reaction conditions are kept so as to achieve a total combustion of 31.19 / *. Cooling is carried out at a distance of 5.638 m from the injection site of the hydrocarbon raw material. The carbon black obtained with good efficiency has an iodine adsorption value of 90, the proper surface determined by the iodine adsorption method 69.3 cm per week, color 2299%, density 304.38 kg / m3, butyl phthalate adsorption value by carbon black granulated 145 cm * / 100 g, and through carbon black 168. Table 4 shows additional properties of the retained carbon black. 108 421 23 24. Example XIV. The procedure of Example XIII is repeated with the difference that the oil feed is introduced at a rate of 590.65 l / h under a pressure of 15.89 kg / cm2 and the auxiliary natural gas in the same amount, i.e. 0.0688 mm / h in which the content is carbon is 5.9% by weight based on the total amount of carbon in the reactants is introduced 0.914 m downstream of the point of injection of the oil feed in the direction of flow. The total combustion is 30% and the cooling is carried out 5.638 m from the point of injection of the primary raw material in the flow direction. The carbon black obtained similarly to Example XIII has the following properties, the iodine adsorption value is 91, the density is 299.5 kg / m2, the specific surface area determined by the iodine adsorption method is 71 m2 / g, the color is 232%. However, while the structure of the carbon black obtained is much higher than that of the control sample, the value of DBP adsorption by the powdery and granular carbon black of Example XIV is lower than by the carbon black of Example XIII. Further properties of the obtained carbon black are illustrated in Table 4. XV. The procedure is as in Example XIII with the difference that the raw oil is injected at 612.9 l / h at a pressure of 17.22 kg / cm2 and the auxiliary natural gas is withdrawn at 0.0688 • 108 m8 / hour at a point 1.219 m from the feed return injection point in the flow direction The carbon content of the auxiliary natural gas is 5.8% by weight based on the total carbon content of the reactants. Total combustion is 29.3% and the reaction is terminated by cooling, which is carried out at a distance of 6.24 m downstream of the point of injection of the primary hydrocarbon feed in the direction of the flow. The soot produced in this way has the following analytical properties - iodine adsorption value 90, density 210.78 kg / m8, specific surface determined by iodine adsorption method 69.3 m2 / g, color 227%. As in the last example, the structure of the carbon black is lower than that of Example XIII. Table 4.1 shows the complete data. From the above data, the introduction of additional natural gas significantly improved the structure of the soot produced. This is evidenced by an increase in DBP adsorption from 10-20 points. It is also evident that the location of the injection of the auxiliary hydrocarbon is of great importance, since the optimal growth of the structure is when the gaseous hydrocarbon is introduced at a point 0.609 m away. from the injection site of the original raw material, the physical properties of the carbon black mixes also improved and, as predicted, the increase in DBP adsorption resulted in the resulting rubber mixes having exceptionally high modules. Example XVI. Examples XVI and XVII show further advantages of using the method according to the invention in obtaining a carbon black with a higher iodine adsorption number and a larger specific surface area than in the previous examples. In the manner described in Example 1, 2.405 · 108 m8 of air preheated to 306.2 ° C and 0.219 · 108 m8 of natural gas are introduced into the combustion zone to obtain a primary combustion of 110%. The hot exhaust gas flows. downward at high linear speed. Table 4 Analytical and physical properties of carbon black Sample of carbon black Iodine adsorption value / acc. To ASTM / Specific surface area determined by iodine adsorption method m2 / g Bulk density kg / m8 Dyeing power% SRF DBP adsorption by granular carbon black cm8 / 100 g DBP adsorption by dusty soot cm8 / g Example 1 'l \ \ 90 | 70 | 328.4 229 124 1149 Example XIII 90 69.3 304.3 229 145 168 Example XIV 91 71 299.5 232 139 163 Example XV | 90 | 69.3 | 3 (10.78 | 227 1 134 | 157 | ^ Natural rubber mixture / NR / * Strength kg / cm2 1 + 20.0 - 9.1 32.3 1.4 32.3 - 9.4 28.1 | —18.2 | Synthetic rubber compound / ISR / *. Module 300% kg / cm2 Strength kg / cm2 Shrinkage after extrusion%, + 38.6 +21.0 91.9 + 54.8 + 3.5 86 , 8. + 61.8 + 6.6 90.5 +51.3 | + 4.9 | 90.2 | * all properties are expressed in relation to carbon black type IRB No. 3.25, then through 4 holes, each with a diameter 0.889 mm oil feed at a pressure of 411.6 l / h under a pressure of 12.86 kg / cm *. The raw material used is the Shamrock tar of Example XIII. The reaction conditions are maintained so as to obtain a total combustion 39.2 Cooling is carried out at a distance of 1.219 m from the point of injection of the oil in the direction of the flow. The soot obtained with good efficiency has an iodine adsorption value of 123, proper surface determined by iodine adsorption method 98 m2 / g, coloration 273 %, density 320.4 kg / m *, butyl phthalate adsorption value by carbon black granules weight is 129 cm8 / 100 grams of carbon black. Additional properties of the obtained carbon black are shown in Table 5, Example XVII. The procedure of Example XVI is repeated with the following exceptions: Air of 2.83 · 10 m * / hour, preheated to 426.6 ° C, is introduced together with 0.238 · 10 * m3 / h of natural gas to obtain a primary combustion of 126%. Shamrock primary hydrocarbon feedstock, in quantity, is introduced into the hot rapidly flowing flue gas. 577.02 L / hr, at a pressure of 21.09 kg / cm2. The raw material is inserted through 4 holes, each 0.940 mm in diameter. It then introduces an additional amount of 111.3 l / h into the flue gas stream. Shanmrock tar, amounts selected so that the carbon content of the auxiliary oil is 13.2% by weight, based on the total carbon content of the reactants. The auxiliary oil was introduced at a point 1.219 m downstream of the feed point through the reactor sidewall using a water cooled sampler equipped with a 60 ° Monarch spray tip with a bore diameter of 0.508 mm. The reactions were conducted with a total percent burn of 36.6% and cooled with water at a point 3.2 meters downstream of the feedstock injection site. A good yield of carbon black with an iodine adsorption value of 116, DBP adsorption by a granular carbon black of 161 cc / 100 g of carbon black is obtained, an increase of 32 points compared to the control of Example XVI. The DBP adsorption value by the dust carbon black is 180. The other data is shown in Table 5. The data in Table 5 also show that the additional amount of hydrocarbon gives a significant increase in the structure of the carbon black. The value of DBP adsorption by the carbon blacks obtained according to the present invention increases significantly. Simultaneously, the modulus and the shrinkage after extrusion of the rubber mixtures will reach the expected values if the low structure carbon black is replaced by the high structure carbon black. 15-55% by weight, expressed as the percentage of carbon in the reactants. In each of the examples, the structure of the carbon black significantly increases, as evidenced by the increase in DBP adsorption 421 26 Table 5 Analytical and physical properties of carbon black Sample 1 Iodine adsorption value Property surface determined by iodine adsorption method m2 / g Dyeing strength% of SRF Adsorption of DBP by granulated carbon black | fcm * / 100 g Adoption of DBP by dusty soot cm * / 100 g Example XVI (123. 98 272 129 H54 Example XVII 116 98 1252 (161 | (180 | Natural rubber mixture / NR / * 'Module 300%, kg / cm2 ^ Strength, kg / cm2 1128.8 +12.6! +32.3 | i— 9.8 1 Synthetic rubber compound / ISR / * Modul 300%, kg / cm2 'Strength, kg / cm2 Shrinkage after extrusion ! +43.5! +22.4 90.2 | +49.2 | (+13.3 | 1 81.9 | * all values are expressed in terms of IRB No.3 carbon black by granulated carbon black by 10-70 points The carbon black of Example XVIII is used as control sample J5. Example XVIII The procedure is as shown in Example I. Air preheated to 426.6 ° C at 9.62 m3 / hr and natural gas a quantity of 0.58 m3 / h is charged to the combustion zone of the reactor. A Gulf Oil Hydrocarbon is introduced into the resulting downwardly flowing stream of hot flue gas at a pressure of 14.06 kg / cm2 and at a quantity of 2,485.2 l. / hour Reactions are carried out in the total The total combustion is 30.7% and the combustion product is cooled with water to a temperature of 700 ° C. Carbon blacks are obtained with a specific surface area of 235 dyeing determined by the method of iodine adsorption 72, DBP 131 adsorption, density 320.5 kg / m * and iodine adsorption 90. The raw material used is Gulf Oil, which is a fuel with 90 carbon content, 3 wt.%, Hydrogen content 7.9 wt.%, Sulfur content 1.9 wt.% 55 wt. The hydrogen to carbon ratio is 1.04, the correlation coefficient is BMCJ 126, the specific gravity according to ASTM D-287 is 1.07, the specific weight in ° APJ according to AiSTM D-287 is 0.4, the viscosity SSU / according to ASTM D -88 / at a temperature of 54.4 ° C is 95.2, and at a temperature of 98.9 ° C it is 40.4 and the content of astoxygen is 2.5%. Supplementary properties of carbon black are presented in Table 6. Example XIX. Following Example I, a primary combustion of 113% is obtained by mixing 2.405 m.sup.8 / hour. preheated 108 421 27 28 to a temperature of 398.8 ° C air and 0.210 · 10 µm1 /. / h of natural gas. Each 0.940 mm diameter of the Sun-ray DX hydrocarbon feedstock described in Example VIII is injected through 4 holes into the hot flue gas. The raw material was introduced at a rate of 536.13 liters / hour under a pressure of 22.4 kg / cm *. Then, similar to the hydrocarbon feedstock, the auxiliary Sunray DX fuel is injected from the circuit into the flue gas stream at a rate of 122.6 liters / hour, which is such an amount that the carbon content of the coal auxiliary is 15.5% by weight in relative to the total carbon content of the reactants, the auxiliary hydrocarbon is introduced at a distance of 0.838 m in the direction of flow from the injection point of the primary raw material. The introduction takes place by injecting the hydrocarbon into the periphery through 4 holes each with a diameter of 0.635 mm at a pressure of 15.46 kg / cms in the transverse direction. The reaction conditions are maintained to obtain a total combustion of 28% / t and the cooling is carried out at a distance of 4.572 m downstream of the injection point of the primary raw material. Further data are presented in Table 6. Example XX. The procedure of Example 19 is repeated with the following exceptions. The raw material is injected at a pressure of 22.84 kg / cm1 through 4 holes each with a diameter of 0.787 mm in the amount of 363.4 l / h. The auxiliary hydrocarbon is introduced in the amount of 272.6 l / h. through 4 openings each with a diameter of 0.635 mm under a pressure of 18.62 kg / cm *. The amount of auxiliary hydrocarbon is such that the carbon content in the auxiliary hydrocarbon is 35.5% in relation to the total carbon content in the reactants. The total combustion is 29.1 wt%, and the cooling takes place at a point 5.181 m from the injection of the raw material. The resultant carbon black is further characterized in Table 6. Example XXI. The procedure is as in Example XX, with the difference that the original raw material is introduced at a rate of 236.2 liters / hour, under a pressure of 18.2 kg / cm, through 4 holes each with a diameter of 0.635 mm. The auxiliary hydrocarbon is also introduced through 4 holes 0.737 mm in diameter at a pressure of 14.76 kg / cmf. The amount of auxiliary hydrocarbon is such that the carbon content is 47.4%, based on the total carbon content of the reactants. The total combustion is 31.8% and the cooling takes place at a location 5.181 m from the injection point of the raw material. The soot retained is described in Table 6. Example XXII. The procedure of Example 19 is repeated with the following exceptions. The hydrocarbon feedstock is introduced from the circumference at a rate of 545.22 l / h under a pressure of 24.6 kg / cm * through 4 holes 0.889 mm in diameter, then added from the circumference through 2 holes 0.635 mm in diameter at a pressure of 2.03 kg / cmf auxiliary hydrocarbon at 113.58 l / h, corresponding to a carbon content of 16.7% by weight, based on the total carbon content of the reactants. In this example, as well as in Examples XXII-XXV, the auxiliary hydrocarbon is introduced at a distance of 1.676 m in the direction l and 18 from the feed injection point. The total combustion is 93.6% and the cooling is carried out at a point of 7.315 meters from the injection point of the raw material. Additional data are presented in Table 6. Example XXIII. The procedure is as in Example XXII, except that the oil is introduced at a rate of 338.47 liters / hour through 4 holes 0.787 mm in diameter at a pressure of 17.22 kg / cm 2. The auxiliary hydrocarbon is introduced through 4 holes 0.635 mm in diameter under a pressure of 11.24 kg / cm 1. As mentioned, the auxiliary fuel is introduced at a point 1.676 m from the feed injection point in the direction of flow. The amount of auxiliary hydrocarbon is such that it has a carbon content of 36.3% relative to the total carbon content of the reactants. Cooling takes place at a distance of 7.315 m from the injection point in the direction of flow. Additional data are presented in Table 6. Example XXIV. The procedure is essentially as in Example XXVII except that the hydrocarbon feed is introduced at a rate of 395.5 l / h through 4 openings of 0.787 mm diameter and a pressure of 22.84 kg / cm1 of auxiliary hydrocarbon is added in the same amount. and place as in example XXII. The carbon content of the auxiliary hydrogen is 34% by weight, based on the total carbon content of the reactants. The total combustion is 32.2% and the cooling takes place at a distance of 7.315 m from the injection point of the oil. The resulting carbon black is described in more detail in Table 6. Example XXV. The procedure is as in Example XXII with the difference that the hydrocarbon feed is introduced in an amount of 513.41 liters / hour through 4 holes 0.838 mm in diameter at a pressure of 23.9 liters / hour. The amount of auxiliary hydrocarbon is injected at a rate of 2 (09.1 l / hour through 4 holes 0.610 mm in diameter at a pressure of 7.03 kg / cm *. The amount of hydrocarbon is such that the carbon content of the auxiliary hydrogen is 24.5 % by weight with respect to the total carbon content of the reactants. As mentioned, the auxiliary hydrocarbon is introduced at a distance of 1.676 m from the point of injection of the feed in the flow direction. Total combustion is 32.7%. 7.325 m from the injection site of the oil raw material. Additional data is presented in Table 6. EXAMPLE XXVI The procedure is as in Example XXV, with the difference that the hydrocarbon feed is introduced in the amount of 154.48 l / hour for 3 holes with a diameter of 0.635 mm, under a pressure of 9.13 kg / cm.sup. The auxiliary hydrocarbon is injected through 4 holes with a diameter of 0.813 mm at a rate of 308.95 liters / hour at a pressure of 13.35 kg / cm1 at a distant point. 1.676 m from the point of injection of the raw oil in the direction of flow. The auxiliary odor is 54.7% by weight, based on the total carbon content of the reactants. Total combustion is 39.7%. Cooling takes place at a distance of 8.686 m from the point of injection of the raw oil in the direction of flow. Detailed data is presented in Table 6.29 108 421 Table 6 Analytical properties of carbon black 30 Carbon black Example | XVIII Example | XIX Example XX Example | XXI Example | XXII Example | XXIII Example 1 XXlv Example | XXV 1 Example 1 xxvi 1 (Iodine adsorption value • 90 91 | 91 | • 88 | • 92 88 | 91 1 '92 90 | Specific surface area determined and iodine adsorption method m2 / g ni 75 76 75 fr5, 77 ¦ 79 i77 71 | Dyeing power fl% SRF 238 J229 246 J236 (234 1 240 • 219 Density kg / m3 (320.6 056.3 12) 40.3 J2f56.3.2-88.3; 256.3. 256.3 .272.3 .288.3 1. Adsorption of DBP by weight granulated cm / 100 g; 101 162 (194 168 150 (202} 192 166 140 Amount of auxiliary hydrocarbon) % Carbon. '(15.5 | £ 5.5 | 47.4 |; 16.7 |. J36.3 34.0 £ 4.5 514.7 Distances from the injection site of the primary raw material to the injection site of auxiliary hydrocarbon m 0.838 0.838 - 1 0.838 0.838 1 1.676- | 1.676 I 1.666 1 1.676 | 1.676 | Physical properties of natural and synthetic rubber mixtures * ¦ Soot sample Ex. XVIII Ex. 1 XIX 1 Ex. XX | Cl. XXI Cl. XXII Cl. XXIII Cl. XXIV Cl. [XXV Cl. Xxvi 1 Natural rubber compound / NR / Strength kg / cmr 1 Module 300 ° / «1 ikg / cm2 | - 4.9 1 +18.2 2 | , + 9.8 | ; + 4i, 4 —33.04 + 69.5 l — 26.3 (+53.7. <+ 4.2 + 35.8 1 —28.4 | 1 + 64.3 —39.3 + 60 , 8 - 34.8 + 50.6 | 15.1 | +42.5 Synthetic rubber compound Strength kg / cm2 'Modul 300% Ikg / cm8 Shrinkage after extrusion ° / o IRB No. 3: + 7 1+ 35.1 r 92 |, + io, i 1 '+67.8 1.85 + 0.7 1 + 99.1 76 + 2.1 i |! +74.8 78 1+ 4.2 / + 53 , 4 and 88 | - 1 | 1 +97 1 1 74 1 - 7 + 81.1 and 75 -112 + 69.5 81 10.1 1 + 63.6 1 82 * all values refer to carbon black type IRB No. 3 The data presented in Table 6 shows that the method according to the invention produces carbon blacks with a high structure by supplying an additional amount of hydrocarbon. At the same time, with appropriate selection of the process conditions, the value of DBP adsorption by the obtained carbon black may increase by 10-20 points. It has been assumed that rubber compounds containing higher structured carbon blacks have a higher modulus value and lower extrusion shrinkage. 65 108 421 31 32 Claims 1. A method for producing furnace carbon black based on this. that in the first stage the fuel and the oxidant are reacted to obtain a stream of fumes with an energy sufficient to convert the liquid hydrocarbon raw material from which the soot is formed, this stream is transferred at a high linear speed to the second a stage in which the liquid hydrocarbon feed is injected into it in the form of a plurality of coherent jets substantially transverse to the flow direction of the gas stream and at a pressure sufficient to obtain the penetration required for proper shearing and mixing, and then in three At this stage, the hydrocarbon feedstock decomposes and is transformed into carbon black before the soot-forming reaction is completed by cooling, and then the carbon black is separated and recovered, characterized by the fact that it goes to the primary reaction zone in the soot formation process in which the previously introduced mixed, atomized and evaporated hydrocarbon raw material undergoes the main production reactions soot particles, and having a distance of 2 - 60 ^ / t between the injection site of the hydrocarbon feedstock and the injection site of the cooling medium, the auxiliary hydrocarbon is introduced in unreacted form and in such an amount that the carbon content in the auxiliary hydrocarbon is 2— - 60% by weight, based on the total carbon content of the reactants, and then cooled. 2. The method according to claim The process of claim 1, wherein the auxiliary hydrocarbon is introduced in liquid form at the point where the hydrocarbon feed is injected. 3. The method according to p. The method of claim 1, wherein the auxiliary hydrocarbon is introduced downstream of the injection site of the hydrocarbon feedstock such that the distance from the injection site of the hydrocarbon feedstock to the injection site of the hydrocarbon feed is 2-60%. from the point of injection of hydrocarbon raw material to the point of injection of the cooling medium. 4. The method according to p. The process of claim 1, characterized in that the auxiliary hydrocarbon is introduced in liquid form in such an amount that its carbon content is 5-6 (M by weight based on the total carbon content in the reactants and in the location downstream of the hydrocarbon injection site). of the raw material so that the distance from the point of injection of hydrocarbon feed to the point of injection of liquid auxiliary hydrogen is 2 to 60% of the distance between the point of injection of the hydrocarbon feed and the point of injection of the cooling medium. A method according to claim 4, characterized in that the auxiliary liquid hydrocarbon is introduced in such an amount that its carbon content is 10-50% by weight, based on the total carbon content of the reactants. , characterized in that the auxiliary hydrocarbon is introduced in a gaseous state in such an amount that its carbon content is 2-10% by weight of the total carbon content in the reactants and at the location in the direction of flow downstream of the injection point of the hydrocarbon feedstock so that the distance from the point of injection of the hydrocarbon feedstock to the point of injection of gaseous auxiliary hydrocarbon is 2-60% of the distance between the point of injection of the hydrocarbon feed and the point of injection of the cooling medium. 7. The method according to p. A process as claimed in claim 6, characterized in that the auxiliary hydrocarbon gas is introduced in such an amount that its carbon content is 4-8% by weight of the total amount of carbon contained in the reactants. 10 15 2 * 2S 3f BLTK 1725/80 r. 110 copies A4 Price PLN 45 PL

Claims (7)

Claims 1. A method for the production of furnace black, which consists in reacting the fuel and the oxidant in the first stage to obtain a stream of flue gas of sufficient energy to convert the liquid hydrocarbon raw material on the carbon black, from which the carbon black is formed. this stream is transferred at high linear speed to the second stage where the liquid hydrocarbon feed is injected into it in the form of a plurality of coherent jets substantially across the direction of the gas stream flow and under a pressure to obtain the degree of penetration required to achieve proper shearing and mixing, whereupon in the third stage the hydrocarbon feed decomposes and is converted into carbon black before the soot reaction is completed by cooling, and then the carbon black is separated and recovered, characterized by the fact that primary reaction zone in the process of soot formation, in which the previously introduced mixed, The atomized and evaporated hydrocarbon feed undergoes the main reactions of the formation of soot particles, and the auxiliary hydrocarbon in unreacted form is introduced at a distance of 2 - 60% / t between the point of injection of hydrocarbon feed and the point of introducing the cooling medium. that the carbon content of the auxiliary hydrocarbon is 2-60% by weight, based on the total carbon content of the reactants, and then cooled. 2. The method according to claim The process of claim 1, wherein the auxiliary hydrocarbon is introduced in liquid form at the point where the hydrocarbon feed is injected. 3. The method according to p. The method of claim 1, wherein the auxiliary hydrocarbon is introduced downstream of the injection site of the hydrocarbon feedstock such that the distance from the injection site of the hydrocarbon feedstock to the injection site of the hydrocarbon feed is 2-60%. from the point of injection of hydrocarbon raw material to the point of injection of the cooling medium. 4. The method according to p. The process of claim 1, characterized in that the auxiliary hydrocarbon is introduced in liquid form in such an amount that its carbon content is 5-6 (M by weight based on the total carbon content in the reactants and in the location downstream of the hydrocarbon injection site). of the raw material such that the distance from the injection point of the hydrocarbon feed to the injection point of the liquid auxiliary hydrogen is 2 to 60% of the distance between the injection point of the hydrocarbon feed and the injection point of the cooling medium. 5. The method according to p. The process as claimed in claim 4, characterized in that the liquid auxiliary hydrocarbon is introduced in such an amount that its carbon content is 10-50% by weight, based on the total carbon content of the reactants. 6. The method according to p. A process as claimed in claim 1, characterized in that the auxiliary hydrocarbon is introduced in a gaseous amount in such an amount that its carbon content is 2-10% by weight of the total carbon content in the reactants and at a point downstream of the injection site of the hydrocarbon feedstock, so that the distance from the point of injection of hydrocarbon feed to the point of introduction of gaseous auxiliary hydrocarbon is 2-60 µm of the distance between the point of injection of the hydrocarbon feed and the point of injection of the cooling medium. 7. The method according to p. A process as claimed in claim 6, characterized in that the auxiliary hydrocarbon gas is introduced in such an amount that its carbon content is 4-8% by weight of the total amount of carbon contained in the reactants. 10 15 2 * 2S 3f BLTK 1725/80 r. 110 copies A4 Price PLN 45 PL