CZ122693A3 - Process for preparing carbon black and novel carbon black - Google Patents

Abstract

Prodn. of carbon black comprises: (a) reacting an oxidant, prim. fuel and carbon black feedstock in a reactor to form an effluent composed of carbon black and combustion gases; (b) injecting an oxidant-contg. stream into the reactor, in order to accelerate the rate of carbon black surface modifying reactions, such that the oxidant stream does not interfere with the formation of the carbon black particles and aggregates in the reactor; (c) passing the effluent through the reactor and (d) cooling, sepg. and recovering the carbon black prod. Carbon black prods. have an iodine number (IN) of 35-65 mg/g, a cetyl-trimethyl ammonium bromide absorption value (CTAB) of 30-55 m2/g, a IN:CTAB ratio of at least 1.12 mg/m2, a Tint value (TINT) of less than 65% and a crushed dibutyl phthalate absorption (CDBPA) value of 75-95 cc/100g. A compsn. contg. rubber and/or a plastic also contains the above carbon black prod.

Description

Method of production of carbon black and new carbon black

Area, techniques

The present invention relates to a novel process for producing retort carbon black and to a class of new retort carbon black. which are suitable for various applications and especially suitable for use in rubber and plastic mixtures.

BACKGROUND OF THE INVENTION

Carbon black is typically produced in a retort reactor by pyrolysis of a hydrocarbon feedstock with hot combustion gases to produce particulate carbon black combustion products. Several methods of carbon black production are generally known.

In one type of reactor for producing carbon black retorts. for example, according to US Patent 3,401,020 to Kester et al. or US 2,785,964 to Pollock, fuel, preferably hydrocarbon, and an oxidizing agent, preferably air, are injected into the first zone where they react to form hot combustion gases. The hydrocarbonaceous feedstock in either the gas, vapor or liquid phase is also injected into the first zone, after which the hydrocarbonaceous feedstock is pyrolyzed. Pyrolysis in this case denotes thermal decomposition of a hydrocarbon. The resulting mixture of combustion gases, in which pyrolysis takes place, then passes to the reaction zone where the carbon black formation reaction is completed.

In another type of reactor for producing the soot retort, the liquid or gaseous fuel reacts with an oxidizing agent, preferably air, in the first zone to produce hot combustion gases. These hot combustion gases pass from the first zone downstream of the reactor to the reaction zone and beyond. In order to produce the carbon black, a hydrocarbon feedstock is injected into the hot gas stream at one or more points of injection. The hydrocarbon feedstock may be liquid. gaseous or steam and may be the same as the fuel used to generate the combustion gas stream or different. Typically, the hydrocarbon feedstock is hydrocarbon oil or natural gas.

However, other hydrocarbon feedstocks such as acetylene are known in the art. The first (combustion) zone may be separated from the reaction zone by strangulation or a reduced diameter zone having a smaller cross section than both the combustion zone and the reaction zone. The feedstock may be injected into the hot combustion gas path in front of, behind, and / or in the zone of reduced diameter. Retort reactors of this type are generally described in US Reissue 28,974 and US 3,922,355.

In the two types of processes and reactors described above, and in other generally known reactors and processes, the hot combustion gases have a temperature sufficient to effect pyrolysis of the hydrocarbon feedstock injected into the combustion gas stream.

In one type of reactor, for example according to Kester, the feedstock is injected at one or more locations into the same zone in which combustion gases are generated. In another type of reactor or process, the feedstock is injected at one or more locations only after the combustion gas stream has been formed.

In both types of reactors, the feedstock is mixed, sprayed and evaporated into the combustion gas stream after the feedstock is introduced. The mixture of combustion gases and vaporized feedstock then enters the primary reaction zone. The term primary reaction zone 'refers to the zone in the process in which the evaporated hydrocarbon feedstock is converted into primary carbon black particles and aggregates. The residence time of the feedstock, combustion gases and soot in the primary reaction zone of the reactor is sufficient to allow soot formation under suitable conditions. A secondary reaction zone may or may not be located downstream of the primary reaction zone in the reactor. In cases of · when..seconds. reaction zone. exists, the term secondary reaction zone denotes the part of the reactor where the surface modification of the carbon black is carried out. formed in the primary reaction zone. The mixture of combustion gases and soot in the secondary reaction zone of the reactor is hereinafter referred to as the " effluent stream. After the carbon black has the desired properties, the temperature of the effluent stream decreases to stop the main reactions. This reduction in temperature and interruption of the main reactions can be accomplished by any known means, for example by injecting a cooling fluid into the effluent stream by a suitable device. As is generally known in the art, the main reactions are interrupted after sampling from the reactor and analytical determination of the properties of the desired carbon black. After interruption of the reactions and sufficient cooling of the effluent stream in any known manner, the effluent stream typically passes through a bag filter or other separator to separate the carbon black.

Two general types of reactors and processes for producing retort carbon black have just been described, but it is understood that the invention is applicable to any other reactor or process for producing retort carbon black where the carbon black is produced by pyrolysis and / or incomplete combustion of hydrocarbons. This procedure differs from the prior art. The process according to claim 1, wherein only an oxidation stream is introduced into the secondary reaction zone in order to accelerate and promote surface modification reactions in the secondary reaction zone.

As used herein, the term oxidation stream refers to any stream containing an oxidizing agent. Preferably, the term oxidation stream refers to air, oxygen-enriched air, combustion products of hydrocarbon fuels, and air and / or oxygen, or mixtures of these streams. This oxidation stream does not interfere with the reactions or processes taking place in the primary reaction zone where primary particles and soot aggregates are formed.

For example, U.S. Pat. Nos. 3,607,058, 3,761,577 and 3,887,690 exist in the prior art. which describe the introduction of secondary heat into a carbon black reactor. This work differs from the invention in that a minimum residence time, determined by increasing the temperature of the effluent stream after the oxidant-containing stream is introduced into the secondary reaction zone, is necessary to achieve the effect of the invention. Neither the residence time nor the minimum temperature rise after the introduction of the secondary heat is specifically described in the cited sources. The analytical properties of the carbon blacks disclosed in the examples of U.S. Pat. No. 3,887,690, in particular the fact that the nitrogen surface area is in all cases greater than the iodine adsorption number, show that the minimum residence time of the invention has not been reached.

Carbon black can be used as pigments, fillers, reinforcing agents and for various other applications. Their use as fillers and reinforcing pigments in the mixing and preparation of rubber and plastic mixtures is widespread. Carbon black is typically characterized by its properties, including, for example, surface size, surface chemistry, aggregate size, and particle size. The properties of the carbon blacks were determined by analytically known assays including iodine adsorption surface area (<12 No), nitrogen surface area (CN2 SA), dibutyl phthalate adsorption (CDBP), dibutylphthalate adsorption (carbon black) (CCTAB), CTINT). , Dmode, and AD50.

It is generally accepted that the properties of carbon black affect the properties of the rubber and plastic compositions containing them. For example, the introduction of carbon black into the rubber or plastic composition during the formation of the composition will generally affect the viscosity of the rubber or plastic composition. Increasing the carbon black content of a rubber or plastic composition normally increases the viscosity of the composition at a given temperature. Low viscosity rubber or plastic compositions are preferred because they are. easy to handle., workable ...

In addition to various applications, such as tires, hoses, belts and plastics, carbon black is typically used in mixtures intended for use as semiconductor shielding compounds for electrical cables. Electrical cables are usually formed by electrically conductive wires surrounded by dielectric insulating material that prevents the leakage of electricity into the environment. These semiconducting shielding compounds are essential for a long cable life, as they reduce the electrical voltage between the conductive and the insulating part of the cable. It is usually desirable to use carbon black in the manufacture of semiconducting shielding compounds for electrical cables. which provide shielding compounds with electrical conductivity. When evaluating the conductivity of a plastic composition, its resistivity is usually measured. However, it is generally accepted that conductivity is a mere inverse of resistivity. The desired degree of conductivity of the shielding composition can be achieved by increasing the carbon black content of the composition, but at the same time increasing the viscosity of the composition. Therefore, it seems advantageous to use carbon black which imparts the desired degree of conductivity while minimizing the viscosity of the composition. The benefits of this optimum combination of properties are not limited to semiconducting shielding materials for electrical cables.

The 300 µm ASTM modulus of the rubber composition is a measure of its stress-strain relationship. The detection of the rubber compound module is described in the ASTM D3192 test. Carbon black is often specified based on its ability to supply the range of module values within certain narrow tolerances. Thus, a process that allows manipulation of the mixture module at a given type of carbon black is advantageous for the carbon black manufacturer. In addition, for certain applications, such as tires for infra-road vehicles, carbon blacks, which impart a low modulus to rubber compositions, are considered to be preferred.

The moisture absorption (CMA) value of a rubber or plastic composition refers to the ability of the composition to absorb moisture. Rubber or plastic compositions which do not absorb moisture are generally desirable for most applications. Therefore, carbon blacks that reduce CMA compositions when incorporated into rubber or plastic compositions are preferred. It is generally believed that lower CMA values are related to lower moisture absorption.

As will be appreciated from the above discussion, it would be advantageous to find a process for the production of carbon black which imparts improved conductivity to plastic or rubber compositions. Further, it would be advantageous to find a group of carbon blacks providing better conductivity and lower viscosity to plastic or rubber compositions. It would also be advantageous to find a process for producing carbon blacks providing lower modulus rubber compositions, lower CMA plastic or rubber compositions and lower viscosity plastic or rubber compositions.

The process according to the invention achieves these advantages among other advantages which will be apparent to those skilled in the art from the following description. Similarly, the carbon blacks of the invention achieve the above advantages and other advantages, which will be apparent from the following description.

SUMMARY OF THE INVENTION

We have found a process for producing carbon blacks of both the conventional type and others which are new, as described below, in which, in order to increase the rate of surface modification reactions in the secondary reaction zone, increase the temperature in the secondary reaction zone without affecting the reactions primary reaction zone. into the secondary reaction zone downstream of the primary reaction zone, an oxidizing stream containing an oxidizing agent such as air, oxygen-enriched air, or hydrocarbon fuel combustion products is injected.

The process is suitable for use in any carbon black reactor wherein the temperature of the effluent stream prior to the injection site of the oxidation stream is greater than 1800 ° F (983 ° C) and less than 2700 ° F (1483 ° C). The point of injection of the oxidation stream is anywhere beyond the primary reaction zone and upstream of the device to interrupt the reactions in the effluent stream. The amount of oxidation stream addition is sufficient to increase the reactor effluent temperature by a minimum value of STSTmin depending on the residence time t after addition of the oxidizing agent and before interruption of the reactions defined as

=ιηίη = 1598 ° F - 6.20 x (t.ms) where

Latitude 110 ° F (43 ° C) a

t> 180 ms

We have also discovered a new class of carbon black with an iodine absorption number (I2 No) of 35 to 65 mg, a CTAB value of 30 to 55 m ² / g and an I2 No / CTAB ratio of at least 1.12 mg / m ² , preferably between

1.12 and 2.20 mg / m ² . especially between 1.12 and 1.50 mg / m ^2, the CDBP value equal to 75 to 95 cm ^3/100 g and tinctorial strength not higher than 65, preferably between 30 and 65%. Furthermore, we have discovered rubber and plastic compositions in which these carbon blacks are incorporated.

The carbon black according to the invention can be produced by the process according to the invention in a retort type reactor having a first (combustion) zone, a feedstock injection zone and a reaction zone consisting of a primary reaction zone and a secondary reaction zone. In the feedstock injection zone, the feedstock providing the carbon black is injected in any known manner into the hot combustion gas stream. The resulting mixture of hot combustion gases and feedstock passes first to the primary reaction zone and then to the secondary reaction zone. The reaction is stopped by cooling the mixture when the carbon black of the present invention is formed. Preferably, the reaction is interrupted by injecting a cooling fluid. The process for preparing the novel carbon blacks of the present invention is described in more detail below.

Rubbers for which the novel carbon blacks of the present invention are effective reinforcing agents include all natural and synthetic rubbers. Generally, about 10 to about 250 parts by weight of the carbon black product may be used per 100 parts by weight of rubber. Preferably, however, an amount in the range of about 20 to about 100 parts by weight of carbon black per 100 parts by weight of rubber is used, and particularly preferred is an amount of about 40 to about 80 parts carbon black per 100 parts of rubber.

Rubbers suitable for use in the present invention include natural rubber and its derivatives such as chlorinated rubber, copolymers of about 10 to about 70% by weight of styrene and about 90 to about 30% by weight of butadiene, such as copolymer of 19 parts styrene and 81 parts butadiene , a copolymer of 30 parts styrene and 70 parts butadiene, a copolymer of 43 parts styrene and 57 parts butadiene and a copolymer of 50 parts styrene and 50 parts butadiene, polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene and the like; a copolymerizable monomer with an ethylene group such as styrene, methylstyrene, chlorstyrene, acrylonitrile. 2-vinylpyridine. 5-methyl-2-vinylpyridine,

-ethyl 1-2-vinylpyridine, 2-methyl-5-vinylpyridine, alkyl 1-substituted acrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, α-methylenecarboxylic acids and their esters and amides such as acrylic acid and dialkylacrylic acid amide; further suitable are copolymers of ethylene and other higher α-olefins such as propylene, 1-butene and 1-pentene; particularly suitable are ethylene-propylene copolymers wherein the ethylene content ranges from 20 to 90% by weight, and furthermore ethylene-propylene polymers which additionally contain a third monomer, such as dicyclopentadiene. 1,4-hexadiene and methylennorbornene.

Any plastic is suitable for use in the present invention. Plastics suitable for use with the novel carbon blacks of the present invention include polyethylene, including ultra-low density, high-density polyethylene, and low-density linear. Also included are copolymers such as ethylene-ethyl acrylates, ethylene-vinyl acetate and ethylene-butyl acrylate. Compositions made of mixtures of the elastomers and plastics described above are also suitable for use.

The advantage is. The novel carbon blacks of the present invention give a lower viscosity than conventional comparable carbon blacks at a given resistivity to the plastic and rubber compositions.

A further advantage is that the process according to the invention produces carbon black which imparts a lower viscosity at a given resistivity to the plastic and rubber compositions.

A further advantage is that the process of the invention produces carbon blacks which deliver a lower modulus at a given proportion of carbon blacks. A further advantage is that the process of the invention can be used to produce carbon blacks that deliver lower CMA (moisture adsorption) to the rubber and plastic compositions.

It is an advantage that the plastic compositions of the invention are particularly suitable for use as a semiconductor shield of electrical cables with improved conductivity and processability characteristics.

Further advantages of the invention will become apparent from a further detailed description of the invention.

Overview of the figure in the drawing

Giant. 1 is a cross-sectional view of a portion of one type of retort carbon black reactor that can be used for the process of the present invention and the carbon black of the present invention. This reactor is used in the examples, but is only a typical example of a usable reactor.

According to the method of the invention, air, oxygen-enriched air, hydrocarbon combustion products and oxygen or other oxidation stream are injected by any known method into a soot-containing effluent stream having a temperature between 1800 ° F (983 ° C) and 2700 ° F before injection. (1483 ° C), in the secondary reaction zone of the reaction vessel downstream of the primary reaction zone in an amount sufficient to increase the effluent temperature by a minimum value of ATmin depending on the residence time t after addition of oxidizing agent and before interruption of reactions defined as

ΔΤηύη = 1598 ° F - 6.20 X (t.ms) where t>; 180 ms a

tpm £ 110 ° F (43 ° C)

The maximum allowable temperature rise is limited by the melting point of the carbon black reactor materials. The maximum residence time is limited by the size of the carbon black reactor.

As one skilled in the art will appreciate, the original feedstock is injected at the point where the soot formation begins. The primary reaction zone refers to that part of the reactor where the hydrocarbon feedstock and combustion gases undergo the main carbon-forming reactions to form primary particles and soot aggregates. This primary reaction zone can be further defined as part of the reactor downstream of the feedstock injection site and in front of where the expanding flue gas stream, feedstock and soot stream exiting the orifice connecting the first stage combustion chamber to the carbon black reactor comes into contact with the wall for the first time soot reactor. In the case of the carbon black reactor shown in FIG. 1, this primary reaction zone (sometimes referred to as the recirculation zone) may be further defined as exiting the carbon black retort inlet to a distance of approximately 3.8 times the retort diameter toward the primary combustion. zone based on the average expansion angle of the expanding stream of combustion gases, feedstock and soot. These definitions of process conditions are illustrated by examples, but are not intended to limit the scope of the invention.

The oxidation stream can be injected by any method known in the art. For example, it is possible to connect the tube to the passage through the reactor wall leading to the secondary reaction zone in the carbon black reactor. and inject the current through this passage. Further, the oxidation stream can be injected further in the process by any known method. The carbon black production method of the present invention is suitable for any carbon black reactor wherein the temperature of the effluent stream from the reactor prior to injection of the oxidation stream is between 1800 ° F (983 ° C> and 2700 ° F (1483 ° C). in an amount sufficient to increase the temperature of the effluent stream by the heat of reaction and / or by cautiously supplying heat by a minimum value depending on the residence time after the addition of oxidizing agent 1 and the interruption of the reactions defined as

ATmin · - 1598 ° F - 6.20 x (t.ms) where t 2: 180 ms a

ATmin £ 110 ° F (43 ° C).

A cross-section of a reactor of the type suitable for carrying out the process of the invention is shown in Fig. 1. It goes without saying that the process of the invention does not require any modification of the carbon black reactor except for the installation of an oxidation stream injection device and therefore can be applied in all types of carbon black reactors. , for example as described in the prior art.

Giant. 1 is a cross-sectional view of a modular (or "stepped") retort reactor for producing carbon black types; described generally in U.S. Pat. No. 3,922,335. Referring to FIG. 1, a carbon black retort reactor 2 is shown. comprising a first stage combustion zone 10 having a tapered diameter zone 11, a feedstock injection zone 12, and a reaction zone 18. The diameter of the combustion zone 10 to the point where zone 11 begins is designated D1, the zone diameter 12 D-2 and the diameter zone 18 D-3. The length of the first stage combustion zone 10 to the point where the zone 11 begins is indicated by L-1, the length of the zone 11 of the tapering diameter L-2, and the length of the feed zone 12 of the feedstock L-3.

The production of carbon black in the combustion zone 10 by contacting a liquid or gaseous fuel with a suitable oxidation stream, such as air, oxygen, air-oxygen mixtures, and the like, produces hot combustion gases. Suitable fuels for use in contact with the oxidation stream in the combustion zone 10 to produce hot combustion gases include any readily combustible gaseous, vapor, or liquid streams such as natural gas, hydrogen, carbon monoxide, methane, acetylene. alcohols or kerosene. However, it is generally preferred to use fuels having a high content of carbonaceous components, in particular hydrocarbons. When natural gas is used to produce the carbon black of the present invention, the air to fuel ratio may be about 10 = 1 to about 100 = 1. To facilitate the formation of hot combustion gases, the oxidation stream may be preheated.

The hot combustion gas stream flows from zones 10 and 11 to zone 12 and then 18. The flow direction of the hot combustion gases is indicated by an arrow in FIG. The carbon black yielding feedstock 30 is fed at point 32 of the inlet. The distance from the end of the tapered diameter zone 11 to the point 32 is denoted F. In the exemplary embodiments, the carbon black yielding feedstock 30 is injected with a plurality of nozzles that extend into the interior regions of the hot combustion gas stream to achieve high mixing intensity and shear forces. hot combustion gases and carbon black yielding feedstock, and therefore rapid and complete decomposition and conversion of the feedstock into carbon black particles and aggregates.

Unsaturated hydrocarbons such as acetylene, olefins such as ethylene, propylene, butylene, aromatics such as benzene, toluene and xylene, certain saturated hydrocarbons and volatiles are suitable as the hydrocarbon feedstock yielding carbon black, which readily evaporates under reactor conditions. hydrocarbons such as kerosines, naphthalenes, terpenes, ethylene tars, aromatic cycle raw materials and the like.

The mixture of the carbon black yielding feedstock and the hot combustion gases passes through zone 12 to zone 18, the carbon black reactor. The reactor according to the invention can usually be divided into two zones: a primary reaction zone and a secondary reaction zone. The primary reaction zone extends in zone 18 from the exit of zone 12 to a distance of approximately 3.8 times the reactor diameter (3.8 times D-3). Air or other oxidation stream is injected into the effluent stream at point 62 via line 60. The axial distance between zone 18 and point 62 is indicated by A and should be at least 3.8 x D-3 in the reactor of Figure 1 to take advantage of the invention. To penetrate the effluent stream, the oxidation stream is injected at a pressure higher than the effluent stream pressure. The oxidation stream can be injected through a nozzle or simply through an orifice.

The coolant injection device 40 located at point 42 is used to stop reactions in the effluent stream. According to the invention, the device 40 is located at point 42, allowing at least a minimum residence time, as defined above, after injection of the oxidation stream through line 60 at point 62.

Q is the distance from the beginning of zone 18 to point 42 and varies according to the location of the quenching site. After quenching the mixture of hot combustion gases and carbon black yielding feedstock, the cooled gases leave to any conventional refrigeration and separation apparatus to recover the carbon black. Separation of the carbon black from the gaseous stream is readily accomplished by conventional means, such as a precipitator, cyclone separator or bag filter. Then he can. but not necessarily, to follow some thickening device, such as pelletizing and drying.

The novel carbon blacks according to the invention are bound by the following characteristics = m ² / g Ϊ2 No with 65 m ² / g 30 m ² / g <CTAB <55 m ² / g

1.12 mg / m ² <ratio I2 No / CTAB tint <65% ^cm3 / 100g <CDBP <95 ^cm3 / 100g In a preferred embodiment, the ratio I2 No / CTAB ranges

1.12 to 2.20, preferably 1.12 to 1.50 mg / m &^lt; ² &gt; We have also discovered new rubber and plastic compositions in which these carbon blacks are incorporated.

The following test procedures are used to determine and evaluate the analytical properties of the carbon blacks of the present invention and the physical properties of the rubber compositions containing the carbon blacks of the present invention, according to the ASTM D3765-85 test procedure. The iodine number (<12 N) of the carbon black is determined by the ASTM D1510 test procedure. The carbon black is determined by the ASTM D3265-85a test procedure. The CDBP value of the carbon black pellets is determined by the test procedure set forth in ASTM D3493-86.

The rubber and plastic compositions of the Examples are evaluated by the following test procedures: The viscosity of the composition is determined according to ASTM D3835-79. The modulus, tensile strength and elongation of the rubber compositions are measured according to the procedures described in ASTM D412. The melt index (MFI) of the compositions is determined according to ASTM D1238-89. Ethylene ethylacrylate (EEA) with an MFI of 6 g / 10 min and a density of 0.931 g / cm ³ is used in the examples. The compositions consist only of carbon black and EEA.

The intrinsic resistivity of the compositions is determined as follows. The internal resistivity (VR) of a sample 'is the product of its electrical resistance (R) and cross-section (A) divided by' its effective length (L), according to the equation

VR = R × A / L

The electrical resistance is determined as follows: a strip of 15.24 cm (6 in) long and 3.81 cm (1.5 in) wide is cut from the extruded strip. For each blend two strips are required, which are cut from the tape so that the length is in the extrusion direction. A silver coating (in this case, DAG 416 from Acheson Dispersions, Port Huron Michigan) at a width of 1.27 cm (0.5 in) is applied to both sides of the strip end. The top, bottom, and edges of the strip are covered in a width of 1.27 cm (0.5 in). After the coating has dried, the width and thickness of the compound and the distance between the surfaces to be coated are measured using suitable instruments. The strips are laid over one 25.4 cm (5 inch) by 16.6 inch (16.4 inch) polycarbonate sheet so that the coated ends are outside the polycarbonate sheet. The strips are adjusted so that they are at least 0.635 cm (0.25 in) apart from each other. - Another polycarbonate foil of the same

- 17 dimensions. Secure both polycarbonate foils with suitable clips. Through the painted areas on the top and bottom of the exposed &quot; ends &quot; of the strips, a straight line of 0.25 inches by 1.27 cm (0.5 in) was applied. Appropriate terminals at the end of the wires are attached to the brass washers. A digital multimeter (in this case Digitec HiO-2120 from United Systems Corp., Dayton, Ohio) should be used to determine the electrical resistance. The unit of electrical resistance is ohm and the unit A, respectively. L, is cm ² , respectively. cm. Therefore, internal resistivity is given in Qcra.

The moisture absorption (CMA) of the compositions is determined by the following procedure: The pre-dried sample of the mixture is placed in a chamber where an atmosphere of constant humidity is maintained for a specified period of time. After this time, the absorption is calculated from the relative weight gain of the composition. Specifically, the procedure is as follows: A 25 g sample of the mixture is granulated in a 4 mm sieve crusher. Take 2 g and dry for a minimum of 2 hours and a maximum of 16 hours under a vacuum of 254 mm (10 in) at 60 ° C (140 ° F). The controlled humidity chamber (for example, Blue fl FR-251B-1 or equivalent) is set at 26.7 ° C (80 ° F) and relative humidity 87. After drying, the samples are placed in this chamber for 7 days, after which time the weight gain is determined using appropriately accurate weights. The CMA value is expressed as the moisture absorption over 7 days at 26.7 ° C (80 ° F) and a relative humidity of 87 based on the original weight.

DETAILED DESCRIPTION OF THE INVENTION.

The invention is further illustrated by means of exemplary embodiments.

In order to demonstrate the efficiency of the invention and the advantages of the novel products obtained by the process of the invention, experiments are carried out on the production of carbon black in the reactor according to the invention, for example of the type shown in FIG. In all of the examples, the primary fuel for the combustion reaction is natural gas supplied to the carbon black formation process at about room temperature (about 298 K ¢ 77 ° F). The liquid feedstock used in all examples is a commercially available mixture of hydrocarbons having the properties listed in Table 1.

Table 1. Properties of the hydrocarbon feedstock

type of raw material AND (B) C D H / C ratio 0.94 0.94 1.03 0.97 hydrogen ¢ ^ wt) 7.20 7.30 8.00 7.51 carbon <3 wt. ) 91.6 92.5 92.4 92.4 API weight - 288.6 / 288.6 K -2.7 3.3 10.4 5.4 BMCI <viscos-wt) 143 132 85 118

Examples 1 to 7

Examples 1 to 7 in Table 2 illustrate the effect of the location of the oxidant addition on the properties of the carbon black. In Examples 1 and 3, air at 0.37 Nm ³ / s (50 KSCFH) and natural gas at 0.015 Nm ³ / s (2.06 KSCFH) are combusted in the first stage combustion zone and the feedstock is injected at point 32 in the amount of 1.4.10 ^-4 m ³ / s g 130 gph). These conditions are kept approximately constant in all of these examples and in any case the effluent stream is cooled at a distance of 14 m (46 ft) beyond the feed point of feed. Example 1 is a control and no additional oxidizing agent is added. The carbon blacks obtained according to Example 1 have an iodine value of 31.7 mg / g, a CTAB of 30.1 m ² / g, a coloring of 39.4% and an iodine value to CTAB ratio of 1.05 mg / m ² . adds to the effluent stream via line 60 at a point 2.44 m <8 ft) downstream of the reactor inlet, preheated to 400 ° C (750 ° F), at a rate of 0.21 Nm ³ / s. This distance is equivalent to 2.7 of the reactor diameter and lies within the primary reaction zone described above and therefore does not meet the criteria of the invention. Carbon black produced according to Example 2. it has an iodine-čfsTo ~ 53v9 mg / GR-CTAB 43.3 m ² /g,-barv.ivo.st61.5% and a CDBP of 68.4 cm ^3/100 g. The relatively large increase in color strength (56 and CTAB (44 together with a large decrease in CDBP compared to Example 1 shows that the addition of an oxidizing agent to the process conflicts with the formation of main particles and soot aggregates that normally take place in the primary reaction zone of the retort. which normally occurs in the primary reaction zone does not affect or disturb.

In Example 3, an additional air oxidation stream is injected into the effluent stream from the reactor at 0.21 Nm ³ / s (28.6 KSCFH) at a distance of 6.86 m (22.5 ft.).

7.5 (reactor diameter) downstream of the reactor inlet, which is clearly in the secondary reaction zone defined above, and downstream of the primary reaction zone in the carbon black reactor shown in FIG. 1. The carbon blacks of Example 3 have an iodine value to CTAB ratio of 1.21 mg. / m ² and a CDBP of 82.8 cm ^3/100 g, Which he values are characteristic of a new class of products. In addition, the color and CTAB values are only slightly different in Example 3 (6 and 6, respectively).

from Example 1, which shows that the addition of an additional oxidizing agent in this case does not interfere with the reactions in the primary reaction zone to form primary particles and soot aggregates. The main effect of adding an additional oxidation stream to Example 3 is to increase the ratio of iodine value to CTAB and to accelerate the reactions typical of the secondary reaction zone in the carbon black reactor.

In Examples 4 and 5, the amount of combustion air in the first stage is 0.37 Nm ³ / s (50 KSCFH5 and the amount of gas in the first stage is 0.015 Nm ³ / s (2.06 KSCFH). 4.10 ^-4 m ³ / s (130 gph) and quench by quenching with water at a distance of 8.54 m (28 ft) downstream of the reactor inlet. In Example 4, no additional oxidant is added to the reactor and the soot low iodine number 31 is added. 3 mg / g, CTAB 31.2 m ² / g, iodine to CTAB ratio of 1.00 mg / m ^2, and dyeing of 40.3¾. In Example 5, air preheated to 400 ° C is used as an additional oxidizing agent ( 750 ° F), which is added to the reactor at 0.21 Nm ³ / s (28.6 KSCFH) at a location 4.42 m (14.5 ft) downstream of the reactor inlet, equivalent to 4.8 of the reactor diameter downstream of the reactor inlet and lie behind the primary reaction zone defined above for the reactor shown in FIG. 1. The carbon blacks obtained in Example 5 have iodine number 42.2 mg / g CTAB 34.7 m ² / g at a ratio of CTAB and iodine number of 1.22 mg / m ² "and the color 43,5¾ bility. Comparison of Examples 4 and 5 shows that the ratio of iodine value to CTAB is significantly increased by the addition of additional oxidizing agent at 4.8 reactor diameter, but CTAB and color change only slightly (by 11% and 8%, respectively). Therefore, the aggregates taking place in the primary reaction zone are not affected by the addition of preheated air at a point remote from the reactor inlet 4.8 of the reactor diameter.

Examples 6 and 7 show that the oxidizing agent can be added at 4.0 reactor diameter downstream of the reactor inlet without substantially affecting the formation of particulate and soot aggregates that take place in the primary reaction zone.

In Examples 6 and 7, combustion air of 0.26 Nm ³ / s (35 KSCFH) and natural gas of 0.012 Nm ³ / s (1.66 KSCFH) are introduced into the first stage combustion chamber. The feedstock is injected in both examples at point 32 in an amount of 0.88.10 ^-4 m ³ / s (84 gph) in Example 6 and 0.99.10 ^-4 m ³ / s (94 gph) of Example 7. A difference in the amount of raw material is necessary to compensate for slight differences in the properties of the feedstock and to achieve a roughly equivalent total burn rate and thus equivalent reaction conditions in the primary zone in both examples. In Example 6, no additional oxidation stream was added to the reactor, and the carbon black obtained was 42 mg / g, 40.3 m ² / g CTAB, 1.04 mg / m ² iodine / CTAB ratio, and dye 53. the oxidation stream uses combustion products of 0.15 Nm ³ / s (20 KSCFH) of air and 0.008 Nm ³ / s (1.09 KSCFH) of natural gas added to the reactor at a distance of 3.66 m (12 ft) downstream of the reactor inlet, which is equivalent to 4.0 reactor diameter downstream of the reactor entrance. A comparison of the analytical properties in Examples 6 and 7 shows that Example 7 has a significantly higher iodine number and iodine number to CTAB ratio, but CTAB and dye are only slightly higher than in Example 6 (by 12 and 4 respectively

This shows that the addition of combustion products at a reactor diameter of 4.0 does not interfere with the formation of particulate and soot aggregates in the primary reaction zone.

Examples 8 and 9

Examples 8 and 9 in Table 2 demonstrate that either air or combustion products of air and natural gas having the same beneficial effect on the carbon black produced can be added to the reactor effluent stream by the method of the invention. In Examples 8 and 9, primary combustion air at a rate of 0.26 Nm ³ / s (35 KSCFH) and natural gas at 0.007 Nm ³ / s (0.92 KSCFH) are fed into the first stage combustion chamber, and the feedstock is added at 32 at 0.86-10 ^-4 m ³ / s (82 gph). In Example 8, an additional 0.13 Nm ³ / s (17 KSCFH) air oxidation stream is added to the reactor effluent stream 4.12 m (13.5 ft) beyond the feed point of feed. Obtained carbon black with an iodine number of 59 mg / g, a CTAB 41.7 m ² / g, a DBPA of 135 cm ^3/100 g. Example 9 into the effluent stream from the reactor the products of combustion are added 0.15 Nm ³ / s (20 KSCFH of air and 0.0075 Nm ³ / s (1.01 KSCFH) of natural gas, providing 100 µl excess air over the stoichiometric amount.

4.12 m (13.5 ft) beyond the feed point. The carbon blacks of Example 9 have analytical properties substantially identical to the carbon blacks of Example 8. In addition, the properties of the mixtures, i.e. the tape resistivity at 90 ° C. MFI and CMA, when mixed with 38% of the carbon blacks of Examples 8 and 9 into the EEA, are also substantially identical. The carbon black of Examples 8 and 9 are further representative of the novel products of the invention.

Examples 10 to 11

Examples 10 and 11 in Table 2 demonstrate that, in order to achieve the desired effects of the invention, an oxidation stream consisting of either the combustion products of air and natural gas or oxygen-enriched air can be additionally supplied in the carbon black reactor. In Example 10, combustion products of 0.23 Nm ³ / s (31 KSCFH) of air and 0.013 Nm ³ / s (1.74 KSCFH) of natural gas are added to the reactor through an inlet located 3.66 m (12 ft) downstream of the reactor inlet to form soot with an iodine value of 58 mg / g and a CTAB of 46 m ² / g at an iodine value to CTAB ratio of 1.23 mg / m ² .

In Example 11, a gaseous stream of 0.056 Nm ³ / s (7.5 KSCFH) of air mixed with 0.011 Nm ³ / s (1.5 KSCFH) of oxygen is added to the reactor to form 34% O 2 through a probe inserted through a wall opening. of the reactor into the secondary reaction zone of the carbon black reactor at a distance of 9.15 m (30 ft) downstream of the reactor inlet. Table 2 shows that the analytical properties of the products in Examples 10 and 11 are very similar and meet the requirements for the improved products of the invention.

Table 2

example- Ϊ 2 3-- 4 '5' 6 Ξ 7 ' D-1, m 0.18 0.18 0.18 0.18 0.18 0.18 0.18 D-2, m 0.11 0.11 0.11 0.11 0.11 0.11 0.11 D-3, m 0.91 0.91 0.91 0.91 0.91 0.91 0.91 L-1, m 0.61 0.61 0.61 0.61 0.61 0.61 0.61 L-2, m 0.30 0.30 0.30 0.30 0.30 0.30 0.30 L-2, m 0.23 0.23 0.23 0.23 0.23 0.23 0.23 F, m 0.11 0.11 0.11 0.11 0.11 0.11 0.11 A, m np 2.44 6.86 np 4.42 np 3.66 Q, m 14.03 14.03 14.03 8.54 8.54 14.03 14.03 spraying of raw materials. 32 32 32 32 32 32 32 nozzle x 9 x 9 x 9 x 9 x 9 x 9 x 9 x size, cm 0.091 0.091 0.091 0.091 0.091 0.091 0.091 raw material flow 1.36 1.36 1.36 1.36 1.36 0.88 0.88 m ³ / s . 10 “« . 10 . 10 “« . 10 ~ « . 10 “« . 10 “« . io ~ « raw material temperature pg 177 177 177 177 177 38 38 type of raw material AND AND AND AND AND C AND addition K + g / m ³ raw. 8.16 8.16 9.16 2.24 2.24 0 0 primary sleep. air, Nm ³ / s 0.37 0.37 0.37 0.37 0.37 0.26 0.26 temp. air, ° C 399 399 399 399 399 510 455 primary natural gas, Nm ³ / s 0.015 0.015 0.015 0.015 0.015 0.013 0.011 air / gas 9.7 9.7 9.7 9.7 9.7 10.0 9.4 secondary air. Nm ³ / sec 0 0.21 0.21 0 0.21 0 0.15 secondary gas, Nm ³ / s 0 0 0 0 0 0 0.01

secondary oxygen, Nm ³ / s 0 0 0 0 0 0 0 temperature increase in zone 2, ° C 0 221 354 0 354 0 147 delay in zone 2, p np 1.03 0.52 np 0.56 np 1.00 temperature chilling, ° C 733 733 733 733 733 733 733 iodine number mg / g 31.7 53.9 39.1 31.3 42.2 42 54 CTAB, m ² / g 30.1 43.3 32.2 31.2 34.7 40.3 45 surface area N 2, m ² / g 27.8 47.5 29.5 36.6 38.0 48.5 I2 / CTAB, rag / m ² 1.05 1.24 1,21 1.00 1.22 1.04 1,2 color,% 39.4 61.5 41.8 40.3 43.5 53 55 DBPA, ^cm3 / 100g 153.2 85.3 133.1 139 133 162 139 CDBP. ^cm3 / 100 g 76.6 68.4 82.8 78.9 76.7 89 88 example 8 9 10 11 D-1, m 0.18 0.18 0.18 0.18 D-2, m 0.11 0.11 0.16 0.11 D-3, m 0.91 0.91 0.68 0.91 L-1, ra 0.61 0.61 0.61 0.61 L-2, ra 0.30 0.30 0.30 0.30 L-3. m 0.23 0.23 0.23 0.23 F, m 0.11 0.11 0.11 0.11 A, ra 4.12 4.12 3.66 4.12 Q. m 14.03 14.03 8.54 14.03 spraying of raw materials. 32 32 32 32 nozzle x 9 x 9 x 9 x 9 X size, cm 0.091 0.091 0.14 0,081 raw material flow 0.86 0.86 1.56 1.18 ra ³ / sec .10- ⁴ . ÍO “ ⁴ .1Q ~ ⁴ . ÍO ⁴

raw material temperature, ° C 93 93 93 93 type of raw material D D AND C at doses Κ *, g / m ³ raw. ...... 0— 0 1, ........... primary sleep. air, Nm ³ / s 0.26 0.26 0.41 0.41 primary air temperature, ° C 399 399 483 483 primary natural gas, Nm ³ / s 0.007 0.007 0.011 0.019 air / gas 9.9 9.9 9.1 9.7 secondary air. Nm ³ / sec 0.13 0.15 0.23 0.06 secondary gas, Nm ³ / s 0 0.008 0.013 0 secondary oxygen, Nm ³ / s 0 0 0 0.011 temperature increase in zone 2 ° C 247 256 225 192 residence time in zone 2, p 1.29 1.15 0.35 0.33 cooling temperature, ° C 733 733 733 733 iodine value, mg / g 56 57 58 56 CTAB, m ² / g 41 42 47 46 N2 surface area. m ² / g 50.5 42.0 51.9 I2 / CTAB, mg / m ² 1.36 1.35 1,23 1,22 color,% 49 49 57 57 DBPA, ^cm3 / 100g 135 134 132 160 CDBP, ^cm3 / 100g 84 84 86 91 filling with soot,% wt. 38.0 38.0 MFI 42.2 42 tape resistivity at 90 ° C, 13, 13, Ocra 800 800 CM A,% 0.12 0.16

nat. rubber module 300% of IRB-6 np = not used

Examples 12 to 17

Examples 12 to 17 in Table 3 illustrate the improved properties of plastic and rubber compositions due to the use of the carbon black produced according to the invention. In these examples, carbon blacks of nearly identical iodine number and DBPA were prepared both with and without the addition of an additional oxidation stream to the process. The carbon black obtained was then blended into the rubber and / or plastic as described above and evaluated for effectiveness.

For the first examples 12 to 15, the natural gas flow into the first stage combustion chamber is 0.015 Nm ³ / s (2.0 KSCFH), the primary combustion air flow is 0.372 Nm ³ / s (50 KSCFH), and the combustion air preheating temperature 399 ° C (750 ° F). The resulting primary combustion value is estimated to be about 250. In all these cases, cooling is performed at a distance of 8.54 m in the reactor. Examples 12 and 14 show control experiments in which a particular iodine number and structure (DBPA) carbon black is produced in the carbon black retort of the carbon black of FIG. 1 without additional oxidant addition. In Examples 12 and 14 were obtained carbon blacks with an iodine number of 42 mg / g and a DBPA of 141 cm ^3/100 g, respectively. an iodine number of 61 mg / g and a DBPA of 133 cm ^3/100 grams. These carbon black are mixed into EEA in the amount of 44% and tested for MFI, Tape resistivity at 90 ° C and CM A. The results of these tests are shown in Table 3. Example 13 and 15 are experiments in which a carbon black having approximately the same iodine number and structure as in Examples 12 and 14 is added with the addition of an additional oxidizing agent of the invention. In these cases, additional preheated combustion air of 0.21 Nm ³ / s is added at a distance of 4.42 m (14.5 ft) after the feed point, and the oil feed rate is adjusted accordingly. to provide the carbon black with the desired iodine number. The obtained carbon blacks of Examples 13 and 15 have almost the same iodine number and DBPA as the carbon blacks of Examples 12 and 12, respectively. 14, but the I2 No / C1AB ratio of the carbon blacks of Examples 13 and 15 is above 1.12 mg / m ² , while the I2 ratio

The N / CTABetazone - from example 12 - is below t, -12 mg / m ^{2 -} a_bárv ivos b ............

in Example 14 is above 65% The carbon black of Examples 13 and 15 is blended into the EEA at 44% and tested for MFI, tape resistivity at 90 ° C and% CMA. By comparing the properties of the compositions of Example 13 with Example 12 and of Example 15 with Example 14 in Table 3, the ratio of tape resistivity at 90 ° C to MFI is found to be much lower in Example 13 than in Example 12 and in Example 15 lower than in Example 14. A lower value of this ratio indicates that the composition has a lower resistivity and a strong viscosity. Further, the composition of Example 13 has a lower CMA than the composition of Example 12, and the composition of Example 15 has a lower CMA than the composition of Example 14.

In Example 16, the conditions in the first stage combustion chamber and feed rate at point 32 are substantially the same as in Example 12. In Example 16, however, 4.42 m (14.5 ft) after the feed point is added to the reactor effluent stream. preheated air at 0.11 Nm ³ / s (14.3 KSCFH). The carbon black produced in Example 16 exhibits analytical properties consistent with the novel products of the invention.

Moreover, the 300% modulus in natural rubber and the 300% modulus in SBR are lower than the properties of similar rubber compositions made with conventional carbon black according to Example 12. As mentioned above, the supply of a low rubber modulus for a given carbon black fill is desirable in many applications.

Example 17 relates to acetylene carbon blacks that are not produced by the retort method and is given for comparison. This material is generally considered to be one of the best types of carbon black available for use in plastic compositions for sheathing medium voltage underground cables. The iodine number, CTAB, dye and CDBP are largely out of range for the novel products of the invention. Resistivity and MFI values of acetylene carbon black at two different fillings are also shown. The filling resistivity at 40% is almost the same as in Example 15 and the filling resistivity at 38% is almost identical to that of Example 13. The MFI is much lower for acetylene black compositions in both cases, indicating that the compositions in Example 17 have a higher viscosity at an equivalent resistivity to Examples 13 and 15.

Table 3

Example 12 13 14 15 16 17 acetylene carbon black

Denka

D-l, m 0.18 0.18 0.18 0.18 0.18 D-2, m 0.11 0.11 0.11 0., 11 0.11 D-3, m 0.91 0.91 0.91 0.91 0.91 L-l, m 0.61 0.61 0.61 0.61 0.61 L-2, m 0.30 0.30 0.30 0.30 0.30 L-3, m 0.23 0.23 0.23 0.23 0.23 F, m 0.11 0.11 0.11 0.11 0.11 A, m np 4.42 np 4.42 4.42 Q, m 8.54 8.54 8.54 8.54 8.54 injection of raw material 32 32 32 32 32 nozzle x 9 x 9 x 9 x 9 x 9 x size, cm 0.091 0.091 0.091 0.091 0.091 raw material flow 1.23 1.36 1.09 1,23 1.23 m ³ / s . 10 ⁴ - 10 “ ⁴ . 10 ~ ⁴ . 10 “ ⁴ . 10 ~ ⁴ raw material temperature, ° C 177 177 177 177 177 type: raw materials AND AND AND AND AND addition of K +, g / m ³ sur. 2.24 2.24 2.24 2.24 2.24

primary air. Nm ³ / sec 0.37 0.37 0.37 0.37 0.37 -teplota prim- ..... - ....... air, ° C 399 399 399 399 -399—— primary earth P1yn, Nm ³ / sec 0.015 0.015 0.015 0.015 0.015 air / gas 9.9 9.9 9.9 9.9 9.9 secondary air, Nm ³ / s 0 0.21 0 0.21 0.11 secondary gas. Nm ³ / sec 0 0 0 0 0 secondary oxygen. Nm ³ / sec 0 0 0 0 0 temperature increase in: zone 2. ° C 0 305 0 316 183 delay in zone 2. p np 0.56 np 0.55 0.69 cooling temperature, ° C 733 733 733 733 733 iodine value, mg / g 42 42 61 63 47 86 CTAB, m ² / g 40 35 54 47 42 75 surface area Na m ² Zg 37.1 36.6 52.8 54.5 41.5 67 12 / CTAB. mg / m ² 1.05 1,2 1.13 1.34 1.12 1.15 color,% 48 44 69 57 53 67 DBPA. ^cm3 / 100 g 141 133 133 127 135 220 CDBP, ^cm3 / 100g 80 77 85 81 79 135 filling with soot. % hm- 44.0 44.0 44.0 44.0 40 38 MFI 13.9 18.5 5.7 10.7 4.0 7.7 tape resistivity 17298 3680 2065 504 443 at 90 ° C. Qcm 3707 CMA,% 0.22 0.12 0.31 0.16 nat. rubber +2.8 -1.5 +0.7

module 300% of IRB-6 np = not used

Examples 18 to 21

Examples 18 to 21 in Table 4 demonstrate the effect of the additional oxidant flow on the analytical properties of the carbon black and the reduction of the modulus of 300% for the rubber obtained from the compositions made with the carbon black. 0.37 Nm ³ / s (50 KSCFH) and natural gas is 0.015 Nm ³ / s (2.06 KSCFH) and point 32, the injected liquid feed in an amount 1,43.10- ⁴ r ³ / s (136 gph) . The only parameter that changes in these examples is the flow rate of superheated air added to the secondary reaction zone in the carbon black reactor to the effluent stream at a location 14.5 ft (4.42 m). ) after entering the reactor. In all of these examples, the reactions were stopped by cooling at a location 8.54 m (28 ft) downstream of the reactor inlet.

Example 18 is a control experiment in which an oxidizing agent is not additionally added to the reactor and the carbon black obtained has an iodine value of 24 mg / g, a CTAB of 28 m ² / g and a 39% dye. In Examples 19, 20, and 21, 0.037 Nm ³ / s (5 KSCFH), respectively, was additionally added to the reactor at a location of 4.42 m (14.5 ft) downstream of the reactor inlet. 0.074 Nm ³ / s (10 KSCFH), respectively. 0.149 Nm ³ / s (20 KSCFH) of air. A comparison of the analytical properties of the carbon blacks of these examples shows that the iodine value increases with increasing flow of additional oxidizing agent. The increasing flow rate of the additional oxidizing agent has substantially little effect on the surface area of the CTAB or dyeing, indicating that the carbon formation reactions in the primary reaction zone were not affected by the increase in oxidant flow rate. A module comparison of 300% for NR and SBR, expressed as a percentage of deviation from the standard sample, for the carbon black containing compositions of these examples, shows that the modulus decreases with an increase in the flow rate of the additional oxidizing agent. As mentioned above, this ability to reduce the rubber modulus is one of the advantages of the method of the invention.

Example 19 with a calculated temperature increase of 43.4 ° C (110 ° F) shows the lowest temperature increase of all examples, demonstrating the advantages of the invention. In addition, the residence time of the effluent stream in the secondary reaction zone of the reactor after addition of the additional oxidizing agent is 0.240 s (240 ms) in Example 19. In Example 21, the calculated temperature increase is 250.2 ° C (482 ° F) and the residence time of the effluent stream in the secondary reaction zone is 180 ms. It can be seen that the chemical reactions in the secondary reaction zone accelerate as the temperature rises. It is also apparent that as the temperature rises, the rate of mixing and diffusion of the oxidation stream with the effluent stream increases. It is therefore clear that the conditions in Examples 19 and 21, where the temperature rise in the secondary reaction zone is the lowest due to the addition of additional oxidizing agent and the shortest residence time in the reactor after addition of secondary oxidizing agent and before cooling (compared to other examples) invention.

Table 4

example 18 19 Dec 20 May 21 D-1, m 0.18 0.18 0.18 0.18 D-2, m 0.11 0.11 0.11 0.11 D-3, m 0.91 0.91 0.91 0.91 L-1, m 0.61 0.61 0.61 0.61 L-2. m 0.30 0.30 0.30 0.30

L-2, m 0.23 0.23 0.23 0.23 F, m 0.11 0.11 0.11 0.11 A, m np 4.42 4.42 4.42 Q, m 8.54 8.54 8.54 8.54 raw material injection, point 32 32 32 32 nozzle x 9 x 9 X 9 x 9 x size, cm 0.091 0.091 0.091 0.091 raw material flow 1.43 1.43 1.43 1.43 m ³ / s . ⁴ ' ⁴ . 10 ~ ⁴ . 10 ~ ⁴ . W ⁴ raw material temperature, ° C 177 177 177 177 type of raw material AND AND AND AND addition of K +, g / m ³ sur. 2.24 2.24 2.24 2.24 primary air, Nm ³ / s 0.37 0.37 0.37 0.37 primary air temperature, ° C 399 399 399 399 primary natural gas, Nm ³ / s 0.015 0.015 0.015 0.015 air / gas 9.7 9.7 9.7 9.7 secondary air, Nm ³ / s 0 0,037 0,074 0.149 secondary gas. Nm ³ / sec 0 0 0 0 secondary oxygen, Nm ³ / s 0 0 0 0 temperature increase in zone 2 ° C 0 43 107 250 residence time in zone 2, p np 0.24 0.22 0.18 cooling temperature, ° C 733 733 733 733 iodine value, mg / g 24 27.1 29 34 CTAB, m ² / g 28 29 29 30 surface area Nz m ² / g 28.2 26.5 28.4 29.2 I2 / CTAB, mg / m and ² 0,857 0.934 1.00 1.13 color,% 39 39 40 40 DBPA, ^cm3 / 100g 150 158 144 145 CDBP, ^cm3 / 100g 83 80 78 77

filling with soot,% wt.

MFI tape resistivity at 90 ° C, Ocm

CM A,% natural. rubber, module 300%,% IRB-6 ......................... 21.7 19.7 17.1 8.3 np = not used

It will be appreciated that these embodiments are illustrative only and not limiting. All modifications within the scope of the claims are within the scope of the invention.

Claims (13)

PATENT Claims ^r . A method for producing carbon black, characterized in that: (a) reacting the oxidizing agent, the primary fuel and the carbon black feedstock in the reactor to produce a effluent stream formed of carbon black and combustion gases; b) an oxidation stream is injected into the reactor to increase the rate of the soot surface modifying reactions without affecting the formation of particulate and soot aggregates; (c) passing the effluent through the reactor; and d) the product is cooled, separated and carbon black is obtained. The method of claim 1, wherein the oxidation stream is injected into the reactor at a point where carbon black particles and aggregates have been formed and where the temperature of the effluent stream in the reactor is between 1800 ° F (983 ° C) and 2700 ° F. <1483 ° C) and in an amount sufficient to increase the reactor effluent temperature by a minimum value depending on the residence time of the carbon black in the reactor after addition of the oxidizing agent, defined as ATmin = 1598 ° F - 6.20 x <t, ms) where ZiTmin (110 ° F <43 ° C) a t> 180 ms where T equals the residence time in milliseconds. The method of claim 2, wherein the oxidation stream is air. The method of claim 2, wherein the oxidation stream is oxygen-enriched air. 5. The method of claim 2, wherein the oxidation stream comprises hot combustion gases of hydrocarbon fuel and air. 6. The process of claim 2 wherein the oxidation stream is the hot combustion products of the hydrocarbon oxygen fuel. 7. The method of claim 2, wherein the oxidation stream comprises hot combustion products of hydrocarbon fuel and air and oxygen. 8. Carbon black, characterized by. they have an iodine value of 35 to 65 mg / g, a CTAB of 30 to 55 m ² / g. Iodine / CTAB ratio of at least 1.12 mg / m ^2, color development of less than 65% and a CDBP of 75-95 cm ^3/100 99. The product according to claim 8, characterized in that the ratio Iodine number / CTAB is from 1.12 to 2.20 mg / m ² . Product according to claim 8, characterized in that the iodine value / CTAB ratio is 1.14 to 1.50 mg / m ² . Product according to claim 8, characterized in that the coloring is 30 to 65%. A composition comprising the rubber, plastic or mixture thereof and the carbon black of claim 8. 9. 10 or 11, wherein the carbon black is present in an amount of 10 to 250 dsk by weight. A composition according to claim 12, wherein the carbon black is present in an amount of 40 to 80 phr. The composition of claim 12, wherein the plastic is ethylene ethyl acrylate.