DD156601A5 - METHOD FOR PRODUCING OVEN SOIL - Google Patents

Abstract

The invention relates to a process for the production of Ofenruss for use as filler, pigment, in particular as an additive for tire carcasses. The aim of the invention is the production of Russians with low structural features. The object of the invention is to produce such Russian with low structural features whose particle size is not significantly increased and which do not contain coke balls. According to the method of the present invention, incomplete combustion of hydrocarbons is carried out by reacting a fuel and an oxidizer in a first stage to produce a stream of combustion gases having sufficient energy to produce a feedstock of liquid hydrocarbon feedstock Russ in a second stage, the liquid hydrocarbon feedstock is injected with pressure in the gas stream and in the reaction mixture in a third zone, the reaction zone, oxidizing agent and hydrocarbons are added in an amount that the equivalency ratio between 1.25 and 0 and then is obtained by quenching soot.

Description

AP C 09 C / 199 505 (51 194 12) 1/4/1978

1 9 9 5 0 5 - '-

Process for the production of furnace black

Field of application of the invention

The invention relates to a process for the production of furnace black for use, for example as pulps and pigments.

In particular, the invention relates to a process for the preparation of semi-reinforcing carbon blacks, for broad use as carbon blacks for tire carcasses.

Characteristics of the known technical solutions

It is known to produce carbon black by cracking and / or incomplete combustion of a liquid hydrocarbon feedstock, for example the cyclic material, in a closed conversion zone at temperatures above 982 C (1800 ⁰ C) (US Patent Application 696771 of 16 ο June 1976).

The resulting soot is initiated by the gases flowing out of the conversion zone, cooled and collected by means of a suitable known means. With the known processes, however, it has been difficult to increase the throughput for producing low structure carbon blacks and semi-reinforcing carbon blacks without altering the essential merlanals of the carbon blacks. In addition, the carbon blacks produced by the known processes are often contaminated with coke balls.

Aim of the invention

The object of the invention is to provide a simple and improved process for the production of carbon blacks with low structural features, which are particularly suitable as additives to tire carcasses.

The invention has for its object to produce by a novel process soot with low structural features so that the particle size is not v / esentlich increased and the recovered carbon blacks do not contain coke balls.

According to the invention, incomplete combustion of hydrocarbons is carried out in such a manner that a certain amount of oxidizing agent, such as air, normally used to carry out the reaction to form the desired carbon black, is disposed at a point downstream of the point. at which the hydrocarbon feed is introduced is added. The introduction of a rope of the required oxidant after the feed material has been injected causes the resulting carbon blacks to have a lower structure but does not significantly increase the particle size of the carbon blacks and may even reduce the particle size.

The amount of oxidant introduced after material injection is between about 5 and about 45 f ° of the total amount of oxidant required to convert the feedstock to the desired carbon black products.

The manner of injection of the oxidizer portion at the downstream location into the resulting soot-containing stream is not critical. For example, the oxidizing agent can be peripheral, longitudinal or

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be introduced tangentially. In a preferred embodiment of the invention, the downstream addition of the oxidizing agent is tangential.

For example, in the case of downstream oxidant injection, it has been found that in addition to reducing the structure of the carbon blacks, the problems of coke and cokeball contamination that accompany the production of oil-reinforcing carbon black in conventional rectors have been alleviated and the yield and carbon efficiency of the process 6 to 10 fo are higher than in the conventional method.

The term "structure" as used herein with respect to carbon black defines a principal property of carbon black that is not consistently affected by a property or combination of properties. "In general, the term is used in the art to indicate the degree of aggregation of the primary particles of a particle To call soot. Since all of the carbon blacks have a certain degree of aggregation of the primary particles, a certain carbon black is classified as low, normal or cooking soot, depending on the degree of aggregation it has shown. The boundaries between the subdivisions in low, hormal or cooking structure are generally not well defined. Conventionally, the structure of the carbon black is considered to be high when the particles have a strong tendency to form particle chains. On the other hand, the carbon black structure is considered to be low when there is a weak tendency to form agglomerates of primary particles. To determine the structure of carbon blacks, a cleavage process using dibutyl phthalate is used here. This method, which is carried out in accordance with ASSM D-2414-72, will be described in more detail below.

Although the direct measurement of the structural features of carbon blacks is possible, there is an equally reliable and

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more suitable method for determining the structural characteristics of carbon blacks accepted in the Pach area and referred to as ASTM Test Method 33-2414-72 entitled "Dibutyl Phthalate Absorption Number of Carbon Black" "In summary, the screening method is that dibutyl phthalate (DBP) to a soot sample in bulk or pelletized Irorm in a Brabender-Cabot absorption meter manufactured and sold by OeW * Brabender Instruments, Ine, South Hackensack, Hew Jersey, and the volume of dibutyl phthalate used is measured is expressed in cubic centimeters or milliliters of dibutyl phthalate (DBP)

per 100 g of carbon black-ramm expressed "Presently, in the ^x art a well-founded ratio with respect to the structural features of a carbon black and the resulting properties of rubber compositions which are mixed with the respective carbon blacks, have been recognized. The ratio is described as one including the degree of structure of a carbon black and the modulus properties of a rubber composition blended with the particular carbon black. It is generally believed that high modulus rubber compositions provide rubber compositions with high modulus values, while using backgraund carbon blacks result in mixed low modulus chewing compositions when all other values are equivalent.

It has been found that the carbon blacks produced by the process of the present invention have significantly lower structural values and that the incorporation of these carbon blacks into ITatures and synthetic rubber compositions results in rubber blends with reduced modulus values.

In particular, semi-reinforcing carbon blacks such as those having iodine adsorption numbers (as defined in ASTM D-I510-70) of between about 28 and about are produced according to the present invention

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A carbon black feedstock is injected substantially transversely into a preformed stream of hot combustion gases which flow at a mean linear velocity of at least 153 m (500 feet) per second in the downstream direction. The feed material is injected transversely from the periphery of the stream into the combustion gases so that penetration is achieved so that coke formation on the walls of the carbon forming zone of the reactor is avoided. The resulting stream then enters the reaction zone whereupon the remaining oxidant needed for the production of the desired carbon black enters the process; is pressed. As noted above, the amount of reaction introduced into the reaction zone varies between about $ 5 and $ 45 of the total amount of oxidant required to produce the desired carbon black. Among the many oxidants suitable for use in this process are air, oxygen and mixtures of air with oxygen at various levels of concentration.

The process of the present invention appreciably reduces the structure of the produced carbon blacks without significantly increasing the particle size of the carbon blacks. When better carbon blacks are blended into rubber compositions, better physical rubber properties are achieved. Λ

The process of the invention will be described in more detail below.

In order to generate the hot combustion gases, which are used in the manufacture of the carbon blacks of the present invention, a liquid or gaseous fuel and a suitable Oxydationsmittelstrom be w% $ air, oxygen, mixtures of air and oxygen o »AEE reacted together in a suitable combustion chamber. To the fuels that are

for the reaction with the Oxydationsmittelstrom in & e ~ £ combustion chamber suitable include all readily combustible gas, vapor or ELüssigkeitsströme such as hydrogen, carbon monoxide, methane, acetylene, alcohols, kerosene. In general <my however, the use of fuels with a high content of carbon-containing components and in particular hydrocarbons is preferred. For example, methane-rich streams such as natural gas and modified or enriched natural gas excellent fuels as well as other gases with a high content of Kohlenv are / asserstoffen how different © hydrocarbon gases and-liquid -% possibilities and refinery by-products including ethane, propane, butane, and pentane fractions, Heating oils etc. »

In the first stage of the process according to the invention, the use of air as the oxidant and natural gas as the fuel for the production of the primary combustion heat is preferred. Under preheater combustion, the amount of oxidant used in the first stage of the process of the invention is to be understood in relation to the amount of oxidant theoretically required for the complete combustion of the first stage hydrocarbon to form carbon dioxide and water. For the sake of simplicity, the primary combustion is expressed as an equivalence ratio. The equivalence ratio is defined as the ratio of the fuel supplied to that required for the stoichiometric combustion of the available oxidant. The percentage of combustion can be calculated from the equivalence ratio by multiplying the inverse of the equivalence ratio by 100. In the present method, the primary combustion can be in the equivalence ratio range of about 1.25 and about 0.33, or in other words, between about 80 and about 300 fo combustion, but the preferred primary combustion is in the equivalent

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Ratio of about 0.83 to about 0.45 or between about 12p and about 220 <$> combustion »

In this way, a stream of hot combustion gases is generated flowing at a high linear velocity. It has been found that a pressure differential between the combustion chamber and the reaction chamber of at least 0.0703 kp / cm (1.0 psi) and preferably about 0.1055 to 0.7031 kp / cm ² (1.5 to 10 psi) is desirable is. Under these conditions, a stream of gaseous combustion products is generated which have sufficient energy to convert a carbon black feed hydrocarbon feedstock into the desired carbon black products. The resulting combustion gas stream from 'the primary combustion zone erreicht- a temperature of at least about 1315 ⁰ C (24-00 ⁰ P), wherein the lowest temperatures at least above about 1650 ⁰ O (3000 ⁰ S ^1). The hot combustion gases are propelled in the downstream direction at a high linear velocity, the velocity being accelerated by the introduction of the combustion gases into a completed smaller diameter transition stage, which may be conical or narrowed if desired, such as by means of a conventional venturi throat constriction becomes. At this very point in the process, which is considered a second stage, the feedstock is vigorously injected into the stream of hot combustion gases.

In particular, in the second stage, where the combustion gases flow at high velocity and have a kinetic gas head of at least greater than 0.0703 kp / cm (1.0 psi), a suitable liquid hydrocarbon feedstock for soot generation is injected into the combustion gases, and although under a pressure sufficient to achieve the desired penetration, whereby a high mixing and shearing effect of the hot combustion gases

and the liquid hydrocarbon refining material. At this time, the liquid hydrocarbon feedstock is rapidly decomposed and converted to carbon black in high yields. As hydrocarbon starting materials which are easy to volatilize under the reaction conditions, are here unsaturated hydrocarbons such as acetylene; Olefins such as ethylene, propylene, butylene; Aromatics such as benzene, toluene and xylene; certain saturated hydrocarbons and volatile hydrocarbons such as kerosenes, naphthalenes, terpenes, ethylene-tars, aromatic cyclic material and the like. suitable"

The liquid feedstock γ / ℓ is injected substantially transversely from the outer or inner periphery of or both into the stream of hot combustion gases in the form of a plurality of small coherent jets which penetrate well into the inner regions or core of the combustion gas stream, but not up to In carrying out the process according to the invention, the hydrocarbon feedstock can easily be introduced as coherent liquid streams by passing the liquid feedstock through a plurality of orifices having a diameter between 0.254 and 3.81 mm (0, 01 and 0.15 inches), and preferably between 0.51 and 1.52 mm (0.02 and 0.06 inches), using an injection pressure sufficient to achieve the desired penetration *

The feedstock used in this case is set with respect to the amounts of fuel and oxidant so that the process for producing carbon blacks an overall equivalence ratio of at least 6.67 and about 2.50, and preferably about _5} 00 and having about 3.33. The G totalaq.uivalenzverhaltn.is is considered to be the

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ratio of the total charged hydrocarbon to that required for the stoichiometric combustion of the available oxidant.

The third stage of the process of the invention involves the provision of a reaction zone which allows a residence time long enough for the soot-forming reaction to proceed by quenching prior to the completion of the reaction. Although the heating time in each pail depends on the particular conditions and the desired specific soot, the residence times in the present process should generally be greater than 15 milliseconds. Once the soot-forming reaction has proceeded for the desired period of time, the reaction is terminated by suspending a quench liquid such as water using at least one set of spray nozzles. The hot effluent gases containing the carbon black products in suspended form are then passed downstream, where the steps of cooling, depositing and collecting the carbon black are carried out in a conventional manner. For example, the deposition of the soot from the grass stream is readily accomplished by conventional means such as a separator, separation cyclone, baghouse filter or a combination thereof.

It has now been found that the structure of the carbon blacks produced by the process according to the invention can be considerably reduced, so that they can be used for those applications in which IT-lower carbon blacks are required. In particular, the structural characteristics of the carbon blacks are reduced by injecting oxidizing agent in an amount between about 5 and 45 # of the total amount of oxidant needed to produce the desired carbon blacks at a point after injection of the liquid coating material into the primary combustion flame follows. The oxidizing agent is

downstream tangentially, peripherally or longitudinally introduced into the reaction zone, the tangential initiation being the preferred mode of operation. The downstream oxidant may be reacted as such or with any suitable liquid or gaseous fuel and introduced into 3 ° C of hot combustion gases. It has been found that in the process of the present invention, the amount of hydrocarbon and oxidant introduced downstream has an equivalence ratio between about 1.25 and about 1.25. may be about 0, with the preferred range being between about 0.46 and 0. All oxidising agents or fuels which may be used for the production of primary brennungswarme. of the method of the present invention are equally suitable for generating the secondary or downstream combustion gas stream, if one is used. In addition, the definition of equivalence ratio for the secondary combustion gas stream is the same. as for the primary combustion heat, with the obvious difference that the ratio is now determined based on the oxidant used and needed downstream. It has also been found that while it may be preferable, but not essential, that the oxidant and / or fuel are the same in producing the two combustion gas streams.

In addition, the equivalence ratio of the primary combustion gas flow may be the same as or different from the equivalence ratio of the secondary or downstream combustion gas flow. j is llemi, for example, implemented a liquid fuel with an oxidizing agent such as air to produce the primary combustion heat, it is possible natural gas react with an oxidizing agent to produce the combustion gases that are introduced after the Beschickungsmat.erialeinspritzung in the reactor. In any case, the combustion gases will be downstream at one

19 9 5 0 5

initiated such that "the structure of the resulting soot is markedly reduced without significantly increasing the size of the carbon blacks"

The following roasting methods are used to evaluate the analytical and physical properties of the carbon blacks produced by the process of the present invention.

iodine adsorption

This is determined according to ASTM D-151O-7O «

Iodine-specific surface _t

The specific surface area of pelletized carbon black products is determined by the following iodine adsorption method.

In this Yerfahren a Eußprob © is given fciegel in a Prozellan- • which is provided with a loosely fitting lid, so that gases can escape, and over a period of 7 minutes at a temperature of 927 ⁰ C 1700 ⁰ F) in a Muffle furnace freed from volatiles, after which they are allowed to cool. The top layer of calcined carbon black is removed to a depth of 6.4 i.mm (1/4 inch) and a portion of the remaining carbon black is weighed.

To this sample is added 100 milliliters of 0.01 N iodine solution. The resulting mixture is stirred for 30 minutes. A 50 ml aliquot of the mixture is then centrifuged until the solution is clear, after which 40 ml of it are titrated using a 1% soluble starch solution as a cross-point indicator with 0.01 N-sodium thio sulfate solution until the free iodine is adsorbed , Dor Percentage of adsorbed iodine is quantified by titration of a carbon black sample. Finally, the iodine-specific surface area, expressed in square meters per gram, is calculated according to the formula / "(percent adsorbed iodine χ 0.937) - 4.5_7 / weight = iodine-specific surface area.

This method of determining the iodine-specific surface area of soot pellets is referred to for convenience as Cabot's test method Hr ₈ "23" 1, since there is no official ASTM name yet ", as published in EC ~ 7O ~ 1 of Cabot Corporation, entitled "Industry Reference Black ITo · 3" (Industry reference Ir * 3) by Juengel and O'Brien, published April 1, 1970, is the iodine-specific surface of IEB Ir 3 (Industrial Reference No 3) 66.5 * n / g as determined by Cabot test method Ir, 23el referred to above * Cj

Debris density, from pellet is inert

It is determined to ASEM D-1513 and recorded as a pound / cubic foot.

Dibutyl phthalate absorption number of carbon black

It is determined according to the ASIM test method D-2414-72 as described above. The results indicate whether the bast is in loose or pelleted form.

The kraft force represents the relative hiding power of a pelletized carbon black when it is in a weight ratio of 1 to 37.5 pounds with a standard zinc oxide (Florence Green 'Seal K'r * 8, manufactured and sold by the New Jersey Zinc Co. ), dispersed in an epoxidized soybean oil plasticizer (Paraplex G-62, manufactured and sold by Rohm and Haas Co.), and compared to a series of standard reference carbon blacks tested under the same conditions.

In particular, the 'test' involves the mulling of carbon black, zinc oxide and plasticizer in such components,

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that the resulting ratio of horsepower to zinc oxide is 1 to 37.5. Roughness measurements using a Welch-Densichron instrument are then obtained from a PiIm cast on a glass plate, and the readings are compared with standard soot tannings with carbon black standards. Soap standards' soot force is determined using an arbitrarily set value of 100 fs for the toning force of Cabot Standard Soot (SEP = Semi-Reinforcing Furnace Black). As is customary, this pail is the standard SRP carbon black, the is arbitrarily assigned a value of 100 fo for the tinting force to Sterling S (Sterling is a registered "" trademark of the Cabot Corporation) or Sterling R semi-reinforcing furnace black produced by the Cabot Corporation Each Sterling-R or Sterling-S reference carbon black is characterized by having, among other features, a nitrogen specific surface area of about 23 Angstroms, an oil absorption of from about 65 to 70 pounds of oil / 100 pounds of carbon black, and one having an average particle diameter of about 800 ingstroms as determined by electron microscopy, the only difference being that the sterling R soot is in loose form, while the Sterling S carbon black is in pelletized form. Accordingly, the soot selected for reference purposes is then determined according to the nature of the soot whose toning force is to be measured γ / ground. The Sterling R or Sterling S semi-reinforcing carbon black is thus considered to be the primary reference standard for determining the oiling power of the other carbon blacks.

In addition, v / ie described above, additional carbon blacks used as Bszugsruße for determining the tint strength values in the range between about 30 ^c ß> and about $ 250. These are determined in relation to the primary standard, which is the arbitrarily set value

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of 100 <fo for the tinting power »became a series. Carbon blacks are provided with a wide range of tinting force values so that reference carbon blacks are present whose values approach as close as possible to the carbon black to be measured. Typical carbon blacks used as auxiliary tinting force standards for the above process are the following ones Penalty imposed on Cabot Corporation ο The analytical values γ / utes are determined according to the test procedures specified in the present application '. ·. '·

Analytical properties

Sterlin MT Sterlin PT (Medium (Pine Thor-Thermal-Soot) mal-Buß)

Vulcan β Η Vulcan 9 '

Tinting power f * 31

Iodine specific surface ra ² / s 5.0

56

DSP absorption

33.6

8.4

35.9

220

110

131

252

119

117

For purposes of illustration, the tinting force of IRB ITr.-3, as determined by the above methods, is 208 f » of primary sterol S semi-reinforcing carbon black. This is disclosed in the publication by Cabot Corporation TG-70-1 entitled "Industry Reference, Black So · 3" (Industrial Reference, Mr. 3); by Juengel and O'Brien, published on April 1, 1970.

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Modulus _r and tensile strength

These physical properties are determined according to the procedures described in ASTM Test Method D-412. Briefly, "modulus casting refers to kp / cm (pounds per square inch) of tension, which is measured when a sample of vulcanized rubber is stretched to 300 'of its original length.The measurement of tensile strength is a determination of the number of kp / cm (Pounds per square inch) of tension required to rupture or break a sample of vulcanized rubber in a tensile test

The invention will be more readily understood with reference to the following examples in which the preparation of representative mixtures is described in detail. There are many other embodiments of this invention. The examples are given for illustration of the invention and should by no means be construed as limiting any of the scope of the invention.

In this example, a suitable reaction facility is terminated which includes means for supplying combustion gas generating reactants, i. of a fuel and an oxidizer, either as separate streams or as pre-combusted gaseous reaction products to the primary combustion zone, and also equipped with means for supplying the carbon feedstock and the combustion gases which are to be introduced downstream into the production plant Reaction equipment may be made of any suitable material, such as metal, and either provided with refractory insulation or by cooling means such as an impeller

199505

Circulatory fluid, 'Preferably water, be surrounded. In addition, the reaction plant is equipped with temperature-around pressure indicating devices, devices quenching the sooting reaction such as spray nozzles, gate directions for cooling the soot product, and devices for 'burning and recovering the soot from other' undesirable by-products. Accordingly, the procedure of the invention is as follows.

In order to obtain the desired heat of combustion of the first stage, in this Palle combustion of 141 ^c ß> or in other words, a Ä ^ uivalenzverhältnis of 0.71, v / ground into a combustion zone of the system by one or more inlets 371 ⁰ C (700 ⁰ P) preheated air at a mean rate of 0.6 nr / hr (75 cubic feet / hour) and natural gas at a mean velocity of 0.048 mVstd (5.67 cf / hr) initiated, producing © in burnt straw which flows at a high linear velocity in the downstream direction. The fast flowing combustion gas stream is directed to a second or transition zone having a smaller cross-sectional diameter to increase the linear velocity of the combustion gas stream. Thereafter, into the resulting stream of hot combustion gases, in the transverse transversal passages through four peripheral feedstreams of 30.40mm (.055 inches) liquid feedstock at a rate of 651.sup.51 (172. 1 gallon) per hour and a pressure of 6.75 at (96 psig, where 1 psig means 7,031.10 at overpressure). The feed material used here (and in all other examples) is Sunray DX, a fuel with a carbon content of 90% by weight, a hydrogen content of 7> 96% by weight, a sulfur content of 1.40%, a hydrogen -Carbon ratio of 1.05 »one

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-· Μ »Ο I. correlation index of 128, a density in accordance with ASTM D-287 of 1.08 of an API density in accordance with ASTM D-287 kit of -0.7, an SSU viscosity. {ASIM D-88) at 55 ⁰ C (130 ° 3?) of 179, an SSU viscosity (ASTU D-88) at 99 ⁰ C (210 ⁰ P) of 46 and an asphaltenes content of 1.9 * ^ The reaction is performed so that the total combustion of the process is $ 23.3, which corresponds to an equivalency ratio of 4.29. Aeration with water to stop the reaction takes place at a point downstream of the feed point of 10,7 m (35 ")."

The analytical values and the performance characteristics of this carbon black are listed in Table 1. In addition, this carbon black is used here as a control for Examples 2 and 3 because the total amount of oxidant was introduced to form the primary combustion heat.

Following the procedure of Example 1, preheated air is introduced into the primary combustion zone at a mean rate of 0.58 mVstd (67.9 eubik feet / hour) and natural gas at a mean rate of 0.043 nr / hr (5.03 cubic feet / hour) to produce the desired Ver ~ incineration of the first stage of 142 _fo} equivalence ratio 0.70. The liquid feed is then introduced at a rate of 646.1 1 (170.7 gallons) per hour and a pressure of 9.07 at (129 psig) through four orifices each having a diameter of 1.3 mm (0.052 Inch). In this example, however, is at a point shortly after the feedstock injection, air at an average rate of 0.06 m / 3TD (7 _r l Kubikf USS / hour), the 9.4 generation $> of the total for the Sr of the desired carbon blacks required Amount of air

The air is reacted with natural gas, which is introduced at a mean velocity of 0.0028 mVstd (0.5 eubikfoot / hour), so that the percentage of combustion of the downstream additive is $ 141 'Equivalent ratio is 0.71, y / as is essentially equal to the percentage of combustion due to primary heat.' The reaction is conducted with a total percentage of $ 23.15> Xquivalence4.26, and the reaction is completed on a Point quenched 10,7 m (35 feet) downstream of feed point for the feedstock. The analytical and physical properties of the carbon blacks are listed in Table 1.

Table I

42 38 29 27 109 104 135 126

Example Ir,

iodine

Iodine-specific. 'Surface, m / g

Soothing power, $> SH3?

DBP absorption, cm ⁵ / l00 g

in pellets

The suitability of the carbon blacks according to the invention as reinforcing agents for rubber compositions is clearly shown by the following examples

In the practice of the examples, the rubber compositions are rapidly made by conventional means. For example, the rubber and the heel used as the reinforcing agent are blended with a conventional blender

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of a type normally used for linting of rubber or plastics, such as a Banbury mixer and / or a roll mill top to ensure the desired dispersion. The rubber compositions are mixed according to standard industrial formulations, for both a natural rubber and a synthetic rubber containing formulation. The resulting Yulkanisate to be treated at 145 ⁰ O (293 ⁰ F) 15 and 30 minutes cured when lTaturkautsch.uk 'is used, and 35', and 50 minutes when a synthetic rubber, in this case, styrene-butadiene Eautschukj is used. To evaluate the performance of the carbon blacks of the invention, the following formulations are used, the amounts being given in parts by weight.

ingredient

Natural rubber formulation

Synthe skaut s chukrezeptur

polymer

Zinc Oxide Sulfur Stearic Acid Altax (MBIS)

I-tart-butyl ~ 2 ~ benzothiäzol-sulfenamide

EUSS

100 natural rubber 100 styrene-butadiene

rubber

5.0 2.5 3.0 0.6

50

3.0

1.75 1.0

1.0 50

~ 20 -

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Physical Properties

Example Mr.

At ltfaturkautsch.uk

300 ^ΰ / ο module, kp / cm ² , 15 minutes + 10.55

$ 300 > module, kp / cm ² , 30 minutes

Tensile strength, kp / cni, 30 minutes

For styrene butadiene rubber extrusion shrinkage, $

$ 300 > module, kp / cm ² , 35 minutes 300 i> module, kp / cm ² , 50 minutes stretch, kp / cm ⁶ ", 50 minutes

Tensile strength, kp / cm,

50 minutes - 87.9 - 84.3

+ 10.55 + 3.52 + 2.82 - 2,82 -44.4 - 35.2 90.4 91.2 - 35.2 - 35.9 ~ 28.1 - 35.2 - 1.41 +0.703

x) All data listed above refer to IR3 ITr. 4 (industrial reference black Br, 4)

The remaining examples are according to Example 1 and. 2 with the exceptions listed in the table below.

'fable II

Example Ir

Primary air medium

Speed '

in mVStd 0.64 0.45 0.64 0.51 0.45

Primary natural gas, m-ystd 0.049 0.034 0.034 0.027 0.024

Primary combustion '-

lq.ui Valence ratio 0.71 0.71 0.80 0.50 0.50 _

Feeding material .. '

1 / hour 575 565 583 600

feed

at 10.2 11.6 10.2 8.3 7.03 '

Opening size, mm 1.40 1.20 1.40 1.32 1.32

downstream, introduced

Air, m-ystd - 0.192 - 0.128 0.3.93

Downstream initiated

Natural gas, m-ystd - 0.010 - 0.0097 0.0145

Downstream Yield - 0.71 - 0.71 0.71

Aq.uivalenzverhältnis

downstream introduced

Oxidizing agent, # - 30 - 20

Gesanitverbremiung 3,89 3 »85 3,73 3,83 3,63

l ^ uivalensverhältnis

Quench, m 10.7 10.7 10 _} 7 10.7 10.7 The analytical data of the above mentioned carbon blacks

and the evaluation of the physical properties are in

of Table III below.

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Table III

Analytical values and physical properties of carbon blacks of Examples 3-7, "with reference to IRB No.

Example Hr, 3 4

Iodine number. 32 39 34 39 38 iodine-specific

Surface area, nr / g 25.8 30 24.2 27.9 29.5 Contraction force, fi SHP 96 115 98 122 119 DBP absorption, om? / 100g

in pellets 144 86 114 90 86

For natural rubber ·

300 fo modulus, kp / cm ²

15 minutes +5.98. -14.1 + 2.82 -7.75 -10.55

$ 300 > module, kp / cm

30 hints -5.28. -27.4 -7P3 -11.95 -16, .9

/ 2 ^Vvi

Tensile strength, kp / cm

30 minutes -56.2 -42.2 -45.8 -21.8 -28.8

For styrene-butadiene rubber

Extrusion shrinkage, <fo 88.6 97.4 92.0 96.6 97.1

300 fo modulus, kp / cm ²

35 minutes -42.9 -71.0 -52.8. -51.3 -59.2

19,950

Portsetsting Table ΙΙΣ

Examples No. _e

300 fo modulus, kp / cm ²

50 minutes -32.4 -56.8 -47.2 -51.4 -57.7

Elongation, kp / eni ² -0.35 + 9.85 +1.41 +5.63 +4.22 '

Tensile strength j kp / cm

50 minutes -105.5 -78.0 -102.0 -64.7 -92.2

In considering the above-mentioned data, Example 1 should be compared with Example 2, Example 3 with Example 4 and Example 5 with Examples 6 and 7. This makes it possible to determine the effects of the method exactly. The most notable feature of the invention is that there is now available a method by which the structural features of a carbon black can be reduced without increasing the rope size of the carbon black. When the invention shows a tendency, it actually appears that the particle size is at all changed - is reduced. This is evident from an overall assessment of the analytical properties of the carbon blacks produced here in comparison with similarly produced but without application of the improvement of the invention, carbon blacks produced.

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From the above data, it can be seen that although all other things are substantially the same, the downstream addition of some of the total amount of oxidizing agent required to produce the desired carbon black in the ice / oil used in this invention results in the production of soot, which has the same or a smaller particle size. This is illustrated by a combination of increasing values for the iodine-specific surface area, tinting strength and iodine number. "The reduction in structural characteristics is manifested not only by the considerable reduction in DBP values, but also by the increased extrusion shrinkage values of styrene-butadiene. Rubber formulations in which the carbon blacks are incorporated. In general, the process according to the invention produces oats which lead to reduced modulus and increased tensile strength in both saturating and synthetic rubbers.

In addition, the method largely solves the problem occasionally encountered in the industrial production of semi-reinforcing carbon blacks, namely the presence of coke balls. «

Another feature of the method according to the invention is

% Yield and carbon efficiency of 6 to 12 fo compared with the conventional process for producing semi-reinforcing carbon blacks.

In this example, a more preferred embodiment of the invention is shown. In this case, the oxidant, namely air, is introduced in its original form and not after prior reaction with a fuel to produce combustion gases, downstream.

While the advantages associated with the use of oxidants in the form of combustion gases, as shown in the previous examples, are retained, the use of pure oxidant in this process is not only a simpler process but also more economical. In this example, another hydrocarbon feedstock, an ethylene process, is used, referred to as imperial steam cracking bottoms. In the Ithylenteer is a fuel with a carbon 'content of 91.2 wt _e $, a hydrogen content of 7.28 wt ^. a sulfur content of 1.2 wt., a hydrogen-to-carbon ratio of 0.95, a 3 -Ii.CI, correlation index of 134, an API density in accordance with ASSM D-237 of -3 , 6, a density "in accordance with ASKI D-287 of 1.11, an SSU viscosity (ASIH D ~ 88) at 54 ⁰ C (130 ⁰ P) of more than 1000, an SSU viscosity (ASKI D). 88) at 99 ⁰ C (210 ⁰ P) of: 106 and a Aphaltgehalt of 19.5 percent,

The procedure of Example 1 is followed, and in accordance therewith are to 288 ⁰ C (550 ⁰ I?) Preheated air at an average rate of 2.25 m / hr (262.9 cubic feet / hour) and natural gas at a middle ^ rate of 0.123 Ö ⁵ / hr initiated (14.4 Kubilrfuß / hour) into the primary combustion zone (> primary combustion or 191 ^c p) to generate the combustion heat of the first stage with a Aquivalenzverliältnis of 0.52, "the feedstock - Ithylenprozeßteer - is then passed through six orifices at a rate of 3130 l / hr (827 gallons per hour) and under a pressure of 12.3 atm (175 psig), four of which have a diameter of 0.101 inches (2.56 mm). and the remaining two have a diameter of 2.89 mm (0.089 inches). At one point in

26 - 19 9 5 0 5

Flow direction after feed injection is at 288 ⁰ C {550 ° 3?) Preheated air tangential with a mean speed of 0,495 m ^ / hr (58.1 cubic feet / hour) in an amount of 18.1 $ for the production of the desired Euß © required total amount introduced into the reaction zone. Potassium chloride is added at a total combustion of 4.43 (or $ 22.5 combustion) equivalence ratio, and quenched at one point 13.1 kg ('43 feet) downstream of the point of feed injection with water.

The nut is produced with a good yield and has an iodine number of 35, an iodine-specific surface area of 28 m / g, a salinity of 121 fo and a DBP absorption (in the case of pellets) of 91 τ / lOq g *

Had this example been carried out without the addition of air downstream, an ejection would have been produced with the same particle size but also with a much higher structure (DBP). * If one had produced a higher structure, and tried would reduce the structure by the addition of potassium chloride to an acceptable level, because such a large amount of potassium chloride would also be required that! tint would be increased to an unacceptable value ₀ Similarly, other oxidants can u including oxygen or oxygen-enriched air "ä. successfully used in the method according to the invention »

While the invention has been described with reference to particular embodiments, it is not limited thereto, and it is to be understood that variations and modifications that would appear obvious to those skilled in the art are possible without departing from the spirit and scope of the invention. The embodiments of the invention in which an exclusive title or privilege is claimed are defined as follows:

Claims (1)

invention claim 1 * A process for the production of furnace black having reduced structural features, characterized by lowered DBP values of the EuBe and increased extrusion shrinkage values of the rubber formations with these fuses, characterized in that a fuel and an oxidizer are reacted in a first stage, so that a stream of combustion gases whose combustion is in the equivalence ratio range of about 1.25 and about 0.33 and which have sufficient energy to convert a carbon black liquid feedstock to carbon black, the combustion gas stream at high linear velocity in the weir a second stage is propelled in which the liquid hydrocarbon feedstock in Porra of a plurality of coherent jets is injected substantially transversely from the periphery of the combustion gas stream © .us and under sufficient pressure into the gas stream to comply with the requirements of US Pat scissors and mixing necessary to achieve the required degree of penetration, the gaseous reaction mixture formed in the downstream direction in a third zone, the reaction zone is introduced, in the oxidizing agent in an amount between about 5 and .about.45 fo that for the production of the desired,. Carbon black, together with an amount of hydrocarbon sufficient to produce an equivalent ratio of between about 1.25 and 100, and terminating the reaction by quenching and recovering the carbon black, the total combustion of the process being in the equivalence ratio range of at least 6.67 to about 2.50. 1 9 9 5 O 5. 2 «method according to item 1, characterized in that
the combustion of the primary combustion gas stream
the first stage in the ÄcLuivalenzverhältnis
from about 0.83 to about 0.46 3 <? Method according to item 1, characterized in that
the oxidizing agent introduced after the feed injection is recovered in the absence of hydrocarbon, so that the equivalent ratio O
is ο A method according to item 1, characterized in that the amounts of oxidant and hydrocarbon introduced after the feed material injection are such that the equivalence ratio is between about 0.46
and O is. 5. The method according to item 1, characterized in that the total combustion for the process in the range of equivalence is from about 6.67 to about 2.50 6, "The method of item .1, characterized in that the overall combustion for the process in the Äquivalenzverhältnisbereioh of about 5.00-to about 33 _3} is' 7o method according to item 1, characterized in that the equivalence ratio of the combustion gases of the first
Stage is substantially the same as the equivalence ratio of the combustion gases _β introduced downstream of the feedstock injection site Qo method according to item 1, characterized in that the oxidizing agent is air. 9 »Method according to item 1, characterized in that the combustion gases are introduced tangentially downstream of the feed material injection site. The method according to item 1, characterized in that the fuel used for the production of the combustion gases of the first stage is a liquid hydrocarbon <