JPS60156763A - Manufacture of carbon black - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the manufacture of racks. These include uses as bulking agents, pigments, and toughening agents in rubber and plastics. Typically, the furnace method for producing carpon black requires a temperature higher than 1256°K (1800"F) to produce carphone black.
It involves the pyrolysis and/or incomplete combustion of a hydrocarbon feedstock, such as natural gas or recycled feedstock, in an enclosed conversion zone. The carpon rack entrained in the gas exiting the conversion zone is then cooled and collected in any suitable equipment commonly used in the industry. However, it is desirable, although difficult, to produce furnace blacks with similar properties that can produce improved hysteresis properties in dem preparations.

It is therefore a principal object of the present invention to provide a new and improved method of producing car blacks which are characterized by properties exhibiting improved hysteresis performance.

Another object of the present invention is to provide crushed DB with low tinting strength.
An object of the present invention is to provide an improved method for producing carbon plaques with high values for P (ODBP).

Another object of the present invention is to improve the coloring strength and OD of carpon racks.
It is an object of the present invention to provide a method for controlling BPO values.

Other and different objects, advantages, and features of the present invention will be apparent to those skilled in the art from consideration of the following detailed description and the appended claims.

In accordance with the present invention, U.S. Reissue Patent No. 28,974
It has now been found that these and further objects are achieved by a complete modification of the modular or staged method of manufacturing car racks of the type disclosed and claimed in this patent. The staging method consists of the first prepared main (first stage) combustion zone, where the high temperature gaseous combustion products are produced, and the liquid hydrocarbon charge is completely combusted in the form of a uniform flow (cohesive jet). A second, or transition zone, injected substantially perpendicularly into the pre-formed hot gas stream from the external or internal periphery of the gas stream, and a second phase where carbon plaque formation occurs, before quenching to terminate the reaction. It consists of three zones (reaction zones).

In methods of the type described above, where the feedstock is injected from around the outside of the combustion gas stream, it is possible for the combustion gas to flow through the device without being used up. This can occur, for example, if the hydrocarbon charge does not completely fill the area through which the combustion gases flow, so that it escapes in the form of unused hot combustion gases. The tendency for this to occur increases as the reactor size increases. In order to prevent this uneconomical combustion from causing loss of gas, U.S. Pat.
No. 5 discloses the injection of additional feedstock into the interior region of the gas stream where combustion is unlikely to arrive with feedstock injected from the outer periphery of the transition zone. In this patent, additional liquid hydrocarbon feedstock is added substantially across the entirety of the combustion gas stream, and in an outward direction from the center of the combustion gas stream, i.e., from the center toward the walls of the reactor. describes the use of appropriate equipment, such as probes, to inject. This makes it clear that the combustion gas is fully used for the purpose of shearing, pulverizing, and dispersing the droplets. The injection into the inner region of the combustion gas stream takes place in the same plane as the plane in which the feedstock is injected from the outer periphery of the transition zone towards the inside of the combustion gas stream. U.S. Patent No. 3,9
The process described in No. 22,335 exhibits very high throughput and high yields, and demonstrates the ability to produce high quality carbon black.

However, it may be desirable to produce carbon black in a manner similar to both methods described above, but with different properties. For details,
It may be preferable to produce all carbon blacks with reduced tinting power and increased 0 DBP, which are indicative of increased repulsion and better hysteretic properties.

In the improved modular 1 or staging method of the present invention, which allows the production of carbon blacks with improved hysteretic properties, the combustion gas stream is substantially radially uniform at locations where the maximum velocity has not been reached. This includes injecting a portion of the liquid hydrocarbon charge into the combustion gas stream as a similar flow.

The raw material to be charged comes from around the outside or inside of the combustion gas stream,
It can be injected substantially radially into the low velocity combustion gas stream. However, it is preferred that the low velocity combustion of the feedstock be injected into the combustion gas stream radially outward from its interior periphery into the combustion gas stream. In the staging method of the present invention, the combustion gas stream reaches its maximum velocity approximately midway through the transition zone. Thus, for example, when injection is being carried out through the probe, the first, i.e. All improvements can be made by drawing the probe into the main combustion zone. The actual point where the raw material is injected into the low-velocity combustion gas stream in the entire radial direction, that is, the plane, is:
There can be considerable variation based on the particular grade or type of carbon black desired. Uniform flow of liquid feedstock The injection of coarse oil droplets radially inward or outward into the low-velocity combustion gas stream is likely to be associated with an increase in the 0DBP value. It is thought that this will result in the generation of

In producing the high temperature combustion gas used in producing the carbon black of the present invention, a liquid or gaseous fuel and a suitable oxidizing gas, such as air, oxygen, a mixture of air and oxygen, etc., are used in a suitable combustion chamber. Makes all body air flow react. Among the fuels suitable for use when high temperature combustion generates gas on reaction with the oxidant stream in the combustion chamber are hydrogen, carbon oxides,
It encompasses any ready-to-combustible gas, vapor, or liquid stream, such as methane, acetylene, alcohol, and kerosene. However, it is generally preferred to use fuels with a high carbon-containing component, and in particular with a high hydrocarbon content. For example, methane-rich streams such as natural gas and modified or fortified natural gas, as well as gases and liquids of various hydrocarbons, and refinery by-products, fuels, including ethane, zolopane, butane and pentane fractions. Other streams containing large amounts of hydrocarbons, such as oil, are excellent fuels.

As far as this specification is concerned, the primary combustion is based on the first stage of the modular method for the amount of oxidant theoretically required to completely burn the first stage hydrocarbons to produce carbon dioxide and water. 1. Shows the general range of oxidants used in history. In this way, hot combustion flowing at high linear velocity generates a gas flow. Furthermore, the pressure difference between the combustion chamber and the reaction chamber is at least 1.0 dend/in2 (6.9 kPa), preferably about 1.5 dend/in2 (10 kPa).
, 3 kilopascals) to about 10 lb/in2 (6
9 kilopascals) was found to be preferable.

These conditions f provide a gas stream of slick combustion products with sufficient coupled energy to pulverize the liquid hydrocarbonaceous feedstock that produces carbon black and produce the desired carbon black product well enough. Generate all. The produced combustion gas stream exiting the main combustion/M zone will have a temperature of at least about 2400"F' (1316°C), most preferably at a temperature of at least about 6000"F' (1316°C).
649"C) Highly engineered. The high temperature combustion gas is provided with an enclosed transition stage of smaller diameter which can be tapered or restricted, if desired, with devices such as conventional Venturi constrictions. It is propelled downstream at a high linear velocity that is accelerated by introducing all the combustion gas into the combustion chamber.

In the method of the present invention, combustion occurs in a uniform flow of some or all of the liquid feedstocks in a substantially radially outward or inward direction from the interior or exterior periphery of the combustion gas stream. It is injected into the combustion gases at a point in the process where the gas stream has not yet reached its maximum velocity, approximately at the midpoint of the transition zone. The remainder of the liquid charge is injected into the combustion gas in the form of a plurality of uniform streams substantially radially, approximately midway through the transition zone, from around the exterior or interior of the combustion gas stream, but not externally. Preferably, it is injected from the periphery.

This technique of full charge injection alters the tinctorial strength and 0 DBP level of the resulting carton black in a direction favorable to improved hysteresis.

In the second stage of the process, the combustion gases flow at a high velocity and the gas velocity head is at least about 1.0 pounds per square inch (
6.9 Pascal). In the transition zone, i.e., the second zone, a portion of the liquid hydrocarbon feedstock forming the carbon black, which is injected in the form of a uniform flow into the combustion gas, undergoes suitable penetration and is injected into the combustion gas at a high temperature. The gas and liquid hydrocarbon feeds must be injected under sufficient pressure to ensure mixing and shearing at high rates. The liquid feedstock is substantially ejected from the periphery of the exterior or interior of the hot combustion gas stream in the form of multiple uniform streams (cohesive jets) that penetrate well into the interior region, i.e., the center, of the combustion gas stream. Inject at right angles to the target.

Suitable for use herein as hydrocarbon feedstocks that are easily volatile under the reaction conditions are unsaturated hydrocarbons such as acetylene, olefins such as ethylene, propylene and butylene, benzene, toluene and aromatics such as xylene, certain saturated hydrocarbons,
and volatile hydrocarbons such as kerosene, naphthalene, turpentine, ethylene tar, and aromatic cyclic feedstocks.

The third stage of the modular process is a reaction zone where the reaction zone is heated to allow sufficient residence time for the black-forming reaction to occur before quenching terminates the reaction. The residence time in each case depends on the particular conditions of the process and the particular carbon black desired.

After the carbon black production reaction has proceeded for a desired period of time, the reaction session is terminated by spraying a cooling liquid, such as water, using at least one full set of spray nozzles. The hot effluent gas containing the suspended carbon black product is then passed downstream where the carbon black is cooled, separated, and collected in a conventional manner. For example, separation of carbon black from a gaseous stream is readily accomplished by conventional methods such as precipitation apparatus, cyclone separators, bag filters, or combinations thereof.

In practicing the present invention, the amount of feedstock injected into the main combustion zone at the point where the combustion gases have reached their maximum velocity may be any amount that results in a total production process of carbon black with increased CDBP values. is the amount or proportion of Additionally, carbon black improves the hysteretic properties of im compositions containing all carbon black. An amount of about 20% to about 80% of the liquid feedstock is injected in a uniform stream into the main combustion zone, and the remaining amount of the charge is injected into the transition zone where the combustion gas stream has reached near maximum velocity. Preferably, it is injected in a single, uniform stream. In a particularly preferred embodiment, from about 40% to about 60% of the charge is injected into the main combustor zone, with the remaining amount of the charge being deposited at a point in the transition zone where the combustion gas stream reaches approximately its maximum velocity. Inject with.

The following test methods are used to quantify the analytical and physical properties of the carbon black produced according to the invention.

Iodine Adsorption Number This is determined according to ASTM D-1510-70.

Coloring power The coloring power of the Carpon Prack sample is ASTM D3265.
-76a, measured in comparison with the industrial color standard Hayabusa black.

Diptyl phthalate (DBP) absorption number The DBP absorption number of Carzen Black is AsTu D 24
14-76. The results recorded indicate whether the carzan black is in fluff-like or granular form.

Fractured DBP Absorption Number (ODBP) Carbon plaque is crushed into small grains after the syllable is treated with A
The structure is determined according to STM D-3493-79.

Modulus and Tensile Strength These physical properties are measured according to the methods described in ASTM D-412. In short, the modulus measurement is related to the tensile force in pounds per square inch that is measured when stretching a vulcanized imum sample to 300 inches of its original length. Tensile strength measurements are made by tearing a vulcanized rubber sample in a tensile test,
That is, it is a measurement of the tensile force required to break in pounds per square inch.

Extrusion Shrinkage This is measured according to ASTM D-2230-37 (Method B).

Repulsion Force This is measured according to the method described in ASTM D-1054.

The present invention will be more easily understood with reference to the following examples. There are, of course, many other forms of the invention that will be apparent to those skilled in the art once the invention has been fully disclosed, and therefore these examples are given by way of illustration only. It will be appreciated that they are not intended to limit the scope of the invention in any way.

Example 1 In this example, combustion reactants that produce gas, i.e.
A device for supplying fuel and oxidant to the main combustion zone, either as separate streams or as pre-combusted but slushy reaction products, and the feedstock until the combustion gas stream reaches maximum velocity. 5. A hydrocarbonaceous feedstock for producing carbon black, which can be moved radially inwardly or outwardly into the combustion gas stream to adjust its injection position, before the injection point. A suitable reactor is used which is also equipped with feeding equipment. The apparatus may be constructed of any suitable material, such as metal, and either be equipped with refractory insulation or surrounded by a cooling system for recirculating a liquid, preferably water. That's it. Additionally, the reactor is equipped with temperature and pressure recording devices, devices for quenching the carbon black production reaction, such as spray nozzles, devices for cooling the carbon black product, and other undesirable sources of carbon black. It is fully equipped with equipment to separate and collect the produced acids. In practicing this embodiment, any suitable burner may be used in the primary or first stage capable of 150% primary combustion. 150%
The combustion gas in the first stage, which is undergoing main combustion, has a velocity of 47
5 standard kilo cubic feet per hour (3,736 m'/sec) and a pre-temperature of 1200'll? Air heated to (922°K) and natural gas at a rate of 62.6 standard kilometers per hour (0,256 m3/s) are charged into the combustion zone of the device at a high linear velocity. In order to increase the velocity below, the cross-sectional diameter flows into the second, i.e. transition zone, where the diameter is smaller. A suitable liquid hydrocarbonaceous charge is then introduced substantially perpendicularly into the generated hot combustion gas stream. The feedstock is passed radially inward from the outer periphery into the center of the combustion gases through 12 unobstructed orifices, each measuring 0.059 inch (1,50 rhymes). Dimensions are 0.059 inches (1
,501) Through six unobstructed orifices,
The combustion gases are injected into the stream in the form of a uniform flow, both radially outward and from the internal periphery.

Therefore, in this operation, a portion of the feedstock is injected outward from the interior periphery of the combustion gas stream, and the remaining 215 is injected inward from the exterior periphery. The injection of all feedstocks is done in the same plane, i.e. approximately at the midpoint of the transition zone, with a merger rate of 9
68I! /hour (1.02 J/sec) and under conditions sufficient to ensure a suitable degree of penetration into the combustion gas stream to ensure that no coke formation occurs within the reactor. The transition zone of the device is 12.4 inches (315y) in diameter.
+m) and has a length of 11 inches (279, ++m). The cross section of the reactor is 18 inches in diameter (4577+I
m, ), and the length before quenching the reaction is 9 feet) (
2-74771).

In the reaction, the total combustion in the process is 26.1%, that is, the equivalence ratio is 6.83, and the position of quenching with water to terminate the reaction is downstream of the position where all the raw materials are injected. Do this so that it is in the ft. position. The analysis and performance characteristics of this carbon black are shown in Table 1. Furthermore, this carbon black is used herein as a control for Example 2, since the feedstock was completely introduced at the midpoint of the transition zone, when the combustion gas stream reached maximum velocity.

Example 2 The method of Example 1 is followed using the same equipment.

The main difference between this example and the method of Example 1 is that the injection of the liquid hydrocarbon feedstock is carried out in the form of a uniform flow radially outward from the internal periphery into the gas stream. Includes all changes in position. In this operation, the injection of a portion of the liquid feed from the internal periphery occurs at a point where the combustion gas stream has not yet reached its maximum velocity, ie before about the midpoint of the transition zone. More specifically,
The main, or first stage, with 247% main combustion (
In order to generate a V-combustion flame, the '12[]
Combustion air heated to 0″F (922°K) is transferred into the main combustion zone at a rate of 475 standard kilometres/hour (3,7
36 m”/sec) and natural gas at a velocity of 19.8 m”/sec).
It is introduced at standard kilo cubic feet per hour (0,156 m3/sec). In this operation, the total rate of liquid hydrocarbon charge combustion injected into the gas stream is 978 g/hr (1,03
A'/sec). Here, as in Example 1,
The liquid feedstock is injected in the form of a uniform stream (collective jet) from the external periphery of the combustion gas stream and from the internal periphery.

More precisely, at approximately the midpoint of the 50% thN transition zone of the feedstock, a radius from the external periphery is drawn through six unobstructed orifices, each measuring 0.110 inch (2,74 mm). Directly inward into the combustion gas stream. The remaining 50% of the liquid charge flows in a uniform flow radially outward from the interior periphery of the combustion gas stream, each dimension 0.113 inches (2,87
mm) into the combustion gas stream through six unobstructed orifices. However, this operation
Injection from the interior perimeter of the liquid feed is 18 inches (457 cm) upstream from the plane where the combustion gas stream reaches maximum velocity.
mu ), ie approximately at the midpoint of the transition zone. The resulting combustion gas stream quenches the carbon black production reaction with water at a location 9 feet (2,74 m) downstream of the plane where the combustion gas stream reaches its maximum velocity, i.e. approximately at the midpoint of the transition zone. into the reaction zone.

The total combustion percentage of the operation is 27.8 inches. The analysis and physical properties of this carbon black are shown in Table 1.

Table 1 Table 2 below demonstrates the suitability of carbon black according to the invention as a low hysteresis reinforcement for im compositions. When calculating carbon black values, it is easy to prepare rubber formulations in a conventional manner. For example, a conventional mixer of the type normally used for mixing imits or plastics, such as a Bunbur 7 mixer and/or a roll mill, to ensure a good dispersion of the emulsions and carton black. Mix thoroughly. The rubber formulations are compounded according to standard industry recipes for natural im or synthetic rubber containing formulations.

The resulting vulcanizate is cured for a period of time defined by measurements of specific physical properties. When determining all numerical values for the performance of the car pump rack according to the present invention, the following formulation defined in terms of tf-parts by weight is used throughout Europe. The im formulation specifically used herein is an ASTM-D-3191-79 synthetic rubber formulation, the characteristics of which are as follows. We present advantageous and surprising results obtained when using it as an additive. The examples, while representative of the invention, should not be construed as limiting or limiting in any way.

3 4 I can understand what is shown. When incorporated into rubber formulations, the repulsion properties are significantly improved which is indicative of an improved history of the rubber vulcanizate.

Although the invention has been described with respect to certain embodiments, it is not intended to be so limited, and changes and modifications that may be apparent to those skilled in the art may be made without departing from the spirit or scope of the invention. Of course it can be done.

Agent Asamura Hajime

Claims (6)

[Claims] (1) In the first zone, the fuel and oxidizer are combined so that a hot primary combustion provides a gas stream with sufficient energy to convert the liquid hydrocarbon feedstock to carbon black. and in the third zone, where the combustion gas stream reaches its maximum velocity, the combustion occurs in a direction substantially perpendicular to the direction of flow of the combustion gas stream.
Moreover, all the liquid hydrocarbon feedstocks are in the form of a uniform stream (cohesive jet) under sufficient pressure to provide the necessary degree of penetration to properly shear and mix the feedstocks. is peripherally injected into the stream of slick combustion products, and in a third zone, the charge is completely decomposed and converted to carbon black before quenching and terminating the carbon-forming reaction, and then: In a modular process for producing furnace carbon black, the carbon black produced is cooled, separated, and harvested. The above method, characterized in that the carbon black is produced by introducing into the air stream substantially radially from the periphery thereof, before the point where the combustion gas stream reaches its maximum velocity, thereby producing a total carbon black with an increased GDPP value. . (2) An amount of about 20 g to about 80 g of the total amount of liquid feed material is injected into the combustion gas stream before the point where the combustion gas stream reaches its maximum velocity, and the remainder is injected into the combustion gas stream where the combustion gas stream reaches its maximum velocity. The method according to item (1) above, wherein the addition is made at the point where the maximum speed is reached. (3) Approximately 40q6 to approximately 60% of the total amount of liquid feed material is injected into the combustion gas stream before the point where the combustion gas stream reaches its maximum velocity, and the remainder is injected into the combustion gas stream at a point where the combustion gas stream reaches almost its maximum velocity. (1) above, which is added at the point where the
The method described in section. (4) Before the point where the combustion gas stream reaches its maximum velocity, the liquid hydrocarbon feedstock to be injected into the combustion gas stream is injected outward from the inner periphery of the combustion gas stream in a substantially perpendicular direction. The method according to item (1) above. (5) The liquid hydrocarbon charge is injected into the combustion gas stream at a point where the combustion gas stream reaches approximately its maximum velocity, inwardly from the outer periphery of the combustion gas stream in a substantially perpendicular direction. Direction as stated in (1). (6) Prior to the point where the combustion gas stream reaches its maximum velocity, the liquid hydrocarbon feedstock to be injected into the combustion gas stream is injected outward from the inner periphery of the combustion gas stream in a substantially perpendicular direction. and the liquid hydrocarbon charge is injected into the combustion gas stream at a point where the combustion gas stream reaches substantially its maximum velocity, inwardly from the outer periphery of the combustion gas stream in a substantially perpendicular direction. The method described in section (1).