WO2022171204A1

WO2022171204A1 - Modified pyrolysis carbon black and preparation method therefor

Info

Publication number: WO2022171204A1
Application number: PCT/CN2022/086733
Authority: WO
Inventors: 马立成; 陈晓燕; 周士峰; 王贝贝; 赵鹏飞; 魏玉山; 孟德营
Original assignee: 双星集团有限责任公司
Priority date: 2021-04-23
Filing date: 2022-04-14
Publication date: 2022-08-18
Also published as: CN113150578A; CN113150578B

Abstract

Provided are a modified pyrolysis carbon black and a preparation method therefor. The modified pyrolysis carbon black comprises, in parts by weight: 100 parts of a pyrolysis carbon residue, 1-5 parts of stearic acid, 0.1-5 parts of a reinforcing resin, 0.1-5 parts of a coupling agent, and 0.1-5 parts of a dispersing agent. The method for preparing the modified pyrolysis carbon black mainly comprises crushing treatment, magnetic separation treatment, pyrolysis carbonization treatment and grinding modification treatment. The present application has characteristics such as a simple operation, a controllable cost, and ideal properties of the carbon black, and can be applied to pyrolysis carbon black manufacturing.

Description

Modified pyrolysis carbon black and preparation method thereof

This application claims the priority of the Chinese patent application filed on April 23, 2021 with the application number 202110443454.6 and the invention titled "A Novel Modified Pyrolysis Carbon Black and Its Preparation Method", the entire contents of which are by reference Incorporated in this application.

technical field

The application belongs to the technical field of pyrolysis carbon black manufacturing and application, and in particular relates to a modified pyrolysis carbon black and a preparation method thereof.

Background technique

With the continuous increase in the use of automobiles, the amount of tires is also increasing, resulting in a large accumulation of waste tires, which in turn brings about a serious "black pollution" problem. At present, pyrolysis technology is the ultimate means to realize the complete recycling of waste tires, which can prepare waste tires into oil, carbon black and steel wire. However, the traditional pyrolysis technology still has defects such as high energy consumption, high cost, low carbon black product yield and unsatisfactory quality.

Therefore, how to develop a new carbon black preparation method with simple operation, low cost and ideal carbon black quality is the key to solving the above problems.

SUMMARY OF THE INVENTION

Aiming at some of the above technical problems, the present application proposes a new type of modified pyrolysis carbon black and a preparation method thereof.

The modified pyrolysis carbon black provided by the first aspect of the application, in parts by weight, includes:

100 parts of pyrolysis carbon residue;

1-5 parts of stearic acid;

Reinforcing resin 0.1-5 parts;

0.1-5 parts of coupling agent; and

0.1-5 parts of dispersant.

Optionally, the modified pyrolysis carbon black, in parts by weight, includes: 100 parts of pyrolysis carbon residue, 4 parts of stearic acid, 2 parts of reinforcing resin, 5 parts of coupling agent and 3 parts of dispersant.

Optionally, the reinforcing resin is selected from at least one of the following groups: UPE resin, 203 resin, 206 resin, and high styrene resin; the coupling agent is selected from at least one of the following group: Si69 coupling agent, Si75 coupling agent, and B69 coupling agent; the dispersant is selected from at least one of the following group: FNS-78T dispersant, BYK-ATU dispersant, and 4170 dispersant.

A second aspect of the present application provides a method for preparing the modified pyrolysis carbon black described in any of the above technical solutions, comprising the following steps:

Crushing treatment: waste tires are first crushed to obtain rubber strips, and the rubber strips are then subjected to second-stage crushing treatment to obtain rubber blocks;

Magnetic separation treatment: the rubber block is subjected to magnetic separation treatment to remove the steel wire in the rubber block to obtain the rubber block after magnetic separation treatment;

Pyrolysis and carbonization treatment: transfer the magnetically-separated rubber block to a cracking device for cracking and carbonization treatment to obtain cracked carbon residue;

Grinding modification treatment: according to the proportion of parts by weight, firstly mix and stir the pyrolysis carbon residue and the coupling agent to obtain a mixture, and then add the mixture, stearic acid, reinforcing resin and dispersant into the grinding machine for The modified pyrolysis carbon black is obtained by grinding and modification treatment.

Optionally, the device used for the first-stage crushing treatment is a strip crusher, and the device used for the second-stage crushing treatment is a granular crusher.

Optionally, the particle size of the glue block is less than or equal to 30 mm.

Optionally, the pyrolysis carbonization treatment is specifically: pyrolysis carbonization treatment at a temperature of 400°C-500°C.

Optionally, the pyrolysis carbon residue and the coupling agent are mixed and stirred in a mixing tank, the stirring temperature is 120°C-150°C, and the stirring time is 0.5-1 h.

Optionally, the grinding modification treatment is specifically: grinding modification treatment at a temperature of 50°C-150°C.

Compared with the prior art, the advantages and positive effects of the present application are:

1. The preparation method of modified pyrolysis carbon black provided by at least one embodiment of the present application, by sequentially performing crushing, magnetic separation, pyrolysis carbonization and grinding modification treatment on waste tires, to prepare a kind of wear resistance, hardness, resistance to The modified pyrolysis carbon black product with ideal properties such as tear strength can be used in the rubber industry such as tires, hoses and conveyor belts;

2. The preparation method of modified pyrolysis carbon black provided by at least one embodiment of the present application has the characteristics of simple operation, short time consumption, controllable cost, etc., realizes the recycling of waste tire rubber resources, and reduces solid waste. pollution to the environment.

Detailed ways

The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

The first embodiment of the present application provides a modified pyrolysis carbon black, which, in parts by weight, includes: 100 parts of pyrolysis carbon residue, 1-5 parts of stearic acid, 0.1-5 parts of reinforcing resin, coupling agent 0.1-5 parts and dispersant 0.1-5 parts. More specifically, it can include: 100 parts of pyrolysis carbon residue, 4 parts of stearic acid, 2 parts of reinforcing resin, 5 parts of coupling agent and 3 parts of dispersant.

The modified pyrolysis carbon black can be used as a product raw material, and is often used in rubber in downstream production processes to further produce other products.

In one embodiment, the reinforcing resin includes, but is not limited to, any one or a combination of UPE resin, 203 resin, 206 resin or high styrene resin. Wherein, the UPE resin is the abbreviation of ultra-high molecular weight polyethylene resin, and its molecular weight is usually between 5 million and 8 million; the 203 resin is the abbreviation of octyl phenolic tackifying resin; the 206 resin is a non-reactive thermoplastic resin The high styrene resin is the emulsion copolymer of styrene and butadiene; wherein, in the copolymer of styrene and butadiene, the styrene content of 50% to 60% is called high styrene rubber , styrene above 70% is called high styrene resin. The reinforcing resin can improve the tensile strength of the obtained modified pyrolysis carbon black product raw material in rubber.

In one embodiment, the coupling agent includes, but is not limited to, any one or a combination of Si69 coupling agent, Si75 coupling agent or B69 coupling agent. Wherein, the Si69 coupling agent is the abbreviation of bis-[γ-(triethoxysilyl)propyl]tetrasulfide; the Si75 coupling agent is the abbreviation of the silane coupling agent CG-SI75; the B69 The coupling agent is the abbreviation of borane coupling agent B69. The main function of the coupling agent is to make the raw material of the modified pyrolysis carbon black product react with the rubber, so as to improve the reinforcing performance of the raw material of the modified pyrolysis carbon black product.

In one embodiment, the dispersants include, but are not limited to, any one or a combination of FNS-78T dispersants, BYK-ATU dispersants, or 4170 dispersants. Wherein, the FNS-78T dispersant is a conventional mixture consisting of a high molecular weight fatty acid ester polymer and an active agent; the BYK-ATU dispersant is a conventional chemical, and the BYK used in this embodiment -ATU dispersant was purchased from Shanghai Puhao Chemical Co., Ltd.; the 4170 dispersant was also a conventional chemical, and the 4170 dispersant used in this embodiment was purchased from Guangdong Lisheng Polymer Technology Co., Ltd. The main function of the dispersant is to help modify the dispersibility of the raw material of the modified pyrolysis carbon black product in the rubber.

It is worth noting that the scope of protection of the present application is not limited to the related products sold by the above-mentioned companies, as long as the raw materials that can meet the relevant properties of the present application can be used.

The application also provides a method for preparing the modified pyrolysis carbon black according to any of the above-mentioned embodiments, comprising the following steps:

S1, crushing treatment: waste tires are first subjected to a first-stage crushing treatment to obtain a rubber strip, and the rubber strip is subjected to a second-stage crushing treatment to obtain a rubber block;

S2, magnetic separation treatment: the glue block is subjected to magnetic separation treatment to remove the steel wire in the glue block to obtain the magnetic separation treatment glue block; the magnetic separation treatment adopts a magnetic separator, which contains magnetic structures such as permanent magnets, The steel wire in the glue block can be adsorbed to remove the steel wire in the glue block.

S3, pyrolysis and carbonization treatment: transfer the rubber block after the magnetic separation treatment to a pyrolysis device, and carry out pyrolysis and carbonization treatment to obtain pyrolysis carbon residue;

S4, grinding modification treatment: according to the proportion by weight, first mix and stir the pyrolysis carbon residue and the coupling agent to obtain a mixture, and then add the mixture, stearic acid, reinforcing resin and dispersant to the grinding machine The modified pyrolysis carbon black is obtained by grinding and modifying treatment in the medium.

In the above technical solution, an embodiment of the present application provides a method for preparing modified pyrolysis carbon black. The grinding particle size of the modified pyrolysis carbon black prepared by the method is controlled between 10 μm and 20 μm, wherein the particle size is between 10 μm and 20 μm. The distribution is obtained by measuring the D90 particle size value with a laser particle size analyzer.

In the above step S4, the reason for mixing and stirring the cracked carbon residue and the coupling agent is that the siloxy groups in the cracked carbon black and the coupling agent need to react under certain temperature conditions and time before the cracked carbon black to modify.

In one embodiment, the device used for the first-stage crushing treatment is a bar crusher, and the device used for the second-stage crushing treatment is a granular crusher.

In one embodiment, the particle size of the rubber block is less than or equal to 30 mm, and processing waste tires into rubber blocks with such a particle size can make them fully react in subsequent pyrolysis carbonization treatment and carbonization treatment, thereby improving the utilization of waste tires. to improve the yield of modified pyrolysis carbon black.

In one embodiment, the pyrolysis carbonization treatment is specifically: pyrolysis carbonization treatment at a temperature of 400°C to 500°C;

In one embodiment, the pyrolysis carbon residue and the coupling agent are mixed and stirred in a mixing tank, the stirring temperature is 120°C-150°C, and the stirring time is 0.5-1 h. Wherein, the stirring temperature can be specifically selected as 120°C, 130°C, 140°C, 150°C, or any value within the above-mentioned limited range selected according to actual needs, all fall within the protection scope of the present application.

In one embodiment, the grinding modification treatment is specifically: grinding modification treatment at a temperature of 50°C-150°C; for example, the selected temperature is 60°C, 80°C, 100°C, 120°C, 140°C, etc. .

In order to introduce the modified pyrolysis carbon black and the preparation method thereof provided by the embodiments of the present application more clearly and in detail, the following will be described with reference to specific examples.

Example 1

The present embodiment provides a preparation method of modified pyrolysis carbon black, the specific contents are as follows:

The modified pyrolysis carbon black formula, in parts by weight, includes: 100 parts of pyrolysis carbon residue, 1 part of stearic acid, 0.1 part of reinforcing resin, 0.1 part of coupling agent and 0.1 part of dispersant. Among them, UPE resin is selected as reinforcing resin, B69 is selected as coupling agent, and FNS-78T is selected as dispersing agent.

The preparation method of modified pyrolysis carbon black comprises the following steps:

(1) crushing treatment: the waste tire first adopts a strip crusher to carry out a one-stage crushing treatment to obtain a rubber strip, and the gained rubber strip adopts a granular crusher to carry out a second-stage crushing treatment to obtain a rubber block, wherein, the rubber block particle size≤30mm;

(2) magnetic separation treatment: the rubber block obtained in step (1) is subjected to magnetic separation treatment to remove the steel wire in the rubber block to obtain the rubber block after the magnetic separation treatment;

(3) pyrolysis and carbonization treatment: transfer the magnetically-separated rubber block obtained in step (2) to a pyrolysis kettle, and conduct pyrolysis and carbonization treatment at 400° C. to obtain pyrolysis carbon residue;

(4) Grinding modification treatment: According to the proportion of parts by weight, first add the pyrolysis carbon residue and coupling agent to the mixing tank, mix and stir at 140 ° C for 0.5 h to obtain a mixture, and then mix the mixture , stearic acid, reinforcing resin and dispersant are added into the grinding machine, and the modified cracking carbon black is prepared by grinding and modification treatment at 50°C.

Example 2

The modified pyrolysis carbon black formula, in parts by weight, includes: 100 parts of pyrolysis carbon residue, 5 parts of stearic acid, 5 parts of reinforcing resin, 5 parts of coupling agent and 5 parts of dispersant. Among them, 2 parts of 203 resin and 3 parts of high styrene resin were selected as reinforcing resin, Si75 coupling agent was selected as coupling agent, and 4170 dispersant was selected as dispersant.

(1) Crushing treatment: waste tires are first crushed with a strip crusher to obtain rubber strips, and the obtained rubber strips are then subjected to a second-stage crushing treatment with a granular crusher to obtain rubber blocks, wherein the size of the rubber blocks is less than or equal to 30mm;

(3) pyrolysis and carbonization treatment: transfer the magnetically-separated rubber block obtained in step (2) to a pyrolysis kettle, and conduct pyrolysis and carbonization treatment at 500° C. to obtain pyrolysis carbon residue;

(4) Grinding modification treatment: According to the proportion of parts by weight, first add the pyrolysis carbon residue and coupling agent to the mixing tank, mix and stir at 150 ° C for 1 hour to obtain a mixture, and then mix the mixture, Stearic acid, reinforcing resin and dispersant are added to the grinding machine, and the modified cracking carbon black is prepared by grinding and modification treatment at 150°C.

Example 3

The modified pyrolysis carbon black formula, in parts by weight, includes: 100 parts of pyrolysis carbon residue, 3 parts of stearic acid, 2 parts of reinforcing resin, 2 parts of coupling agent and 2 parts of dispersant. Among them, 206 resin is selected as reinforcing resin, Si69 coupling agent is selected as coupling agent, and BYK-ATU dispersant is selected as dispersant.

(4) Grinding modification treatment: According to the proportion of parts by weight, first add the pyrolysis carbon residue and coupling agent to the mixing tank, mix and stir at 150 ° C for 1 hour to obtain a mixture, and then mix the mixture, Stearic acid, reinforcing resin and dispersant are added to the grinding machine, and the modified cracking carbon black is prepared by grinding and modification treatment at 80°C.

Film preparation and performance testing

In this application, in order to verify the properties of the modified pyrolysis carbon black prepared in the above examples, in this test experiment, it is used as a raw material to prepare a film, and various performance tests are carried out on the obtained film to evaluate the modified pyrolysis carbon. Whether the performance of the black is up to expectations. This performance test experiment consists of 2 groups of experimental groups and 2 groups of control groups. The film formulations and preparation methods are as follows:

Film formulations, as shown in the table below:

Table 1 Film formulations of experimental group and control group

Note: The pyrolysis carbon black corresponding to No. 3 is obtained by grinding the pyrolysis carbon residue obtained in step (3) in the preparation method described in Example 3 of the present application; The modified pyrolysis carbon black prepared by the preparation method. Both experimental group 1 and experimental group 2 used the modified pyrolysis carbon black of Example 3; the experimental effects of using other embodiments were similar to those of Example 3, and will not be repeated.

The preparation method of the film, the experimental group and the control group are all carried out according to the following preparation method, including the following steps:

(1) One-stage mixing: add natural rubber SMR20 into the internal mixer, and control the speed of the internal mixer at 45r/min, pressurize and mix → add stearic acid, zinc oxide, and antioxidant RD to it Continue mixing with 6PPD for 45s→then add carbon black and aromatic oil according to the raw material formula in Table 1, and control the temperature at 130℃ for 65s→lifting and pressing→mixing at 150℃ for 60s→lifting and pressing Mass → kneading at 160°C for 60 s, lifting the mass and discharging to obtain master rubber → the master rubber is thinly passed three times in the opener, and the lower piece is parked for 4 hours to obtain a section of rubber;

(2) Two-stage mixing: add the first-stage rubber compound obtained in step (1) into the internal mixer and mix for 20s → then add accelerator NS and insoluble sulfur to it and continue to mix for 20s → lift the weight and press the weight → at a temperature of 105 ° C After kneading for 40 s under the conditions, the mass is lifted and discharged to obtain the final rubber compound → the final rubber compound is thinly passed three times in the opener, and the lower sheet is used for later use. (The roll distance is 0.6-0.8mm) three times, and the thickness of the sheet is 1.8+/-0.2mm;

(3) Vulcanization: Cut the kneaded film in step (2) according to the sample preparation requirements, and then set the vulcanization conditions for the flat plate vulcanizer. After reaching the set temperature and stabilizing for 0.5h, put the sample into vulcanization, and after the vulcanization is completed, take it out and park it for 24-48h test;

(4) Test: Prepare test samples according to the sample preparation requirements in the national standard GB/T528. The samples are tested according to the requirements of the national standard, and the test results are shown in the following table:

Table 2 Vulcanization properties of experimental group and control group films

As can be seen from the data in Table 1, the carbon blacks used in the control group 1-2 are carbon black N330 and cracked carbon black, wherein, carbon black N330 is conventional industrial carbon black, and cracked carbon black is the step in the preparation method described in Example 3 of the application. (3) the obtained pyrolysis carbon residue is simply ground and obtained, it can be seen from this that the carbon black used in the control group 1-2 is the traditional industrial carbon black, and the carbon black used in the experimental group 1-2 is the use of the examples of the application The modified pyrolysis carbon black prepared by the method described in 3.

On the basis of the above content and in combination with the data in Table 2, it can be seen that the films prepared in experimental groups 1-2 (that is, films with the modified pyrolysis carbon black prepared in the examples of the present application added in the preparation process) have a higher level of Mooney viscosity, Mooney Joule The characteristics of burning time, vulcanization rate, processing safety and other characteristics are basically the same as those of the control group, which indicates that the modified pyrolysis carbon black prepared by the present application can replace the use of traditional industrial carbon black, and the processing characteristics of the obtained film are improved. no effect.

Table 3 Physical and mechanical properties of experimental group and control group films

Table 3 shows the test results of the physical and mechanical properties of the experimental group and the control group. It can be seen from the data shown in Table 3 that, compared with the control group 1, the films made by the experimental group 1 (that is, the films prepared by adding the embodiment of the present application during the preparation process) The obtained modified pyrolysis carbon black film, in parts by weight, the addition amount is 15 parts), the tensile strength is increased by about 3%, the 300% tensile stress is increased by 5%, the hardness is increased by 0.1 degrees, and the tear strength is increased by 4%. %, the wear resistance is improved by 5%, and the overall performance is improved by 4% compared to the standard compound shown in Control 2. Compared with the control group 2, the film made by the experimental group 2 (that is, the film added with the modified pyrolysis carbon black obtained in the embodiment of the present application in the preparation process, in parts by weight, the addition amount is 25 parts) stretched. The strength is increased by 10%, the 300% tensile stress is increased by 10%, the hardness is increased by 1.5 degrees, the tear strength is increased by 9%, and the wear resistance is increased by 8%. The overall performance is 9% better than the standard compound shown in Control 2.

Compared with the control group 2, the film prepared in the experimental group 1 (that is, the film added with the modified pyrolysis carbon black prepared in the embodiment of the present application in the preparation process, in parts by weight, the addition amount is 15 parts) stretched. The strength is increased by about 25%, the 300% tensile stress is increased by 20%, the hardness is increased by 3 degrees, the tear strength is increased by 25%, the wear resistance is increased by 36%, and the overall performance is 25% higher than that of the standard compound shown in Control 2. Compared with the control group 2, the film made by the experimental group 2 (that is, the film added with the modified pyrolysis carbon black obtained in the embodiment of the present application in the preparation process, in parts by weight, the addition amount is 25 parts) stretched. The strength is increased by 30%, the 300% tensile stress is increased by 28%, the hardness is increased by 3 degrees, the tear strength is increased by 30%, and the wear resistance is increased by 38%. The overall performance is 31% higher than the standard compound shown in Control 2. It can be seen that, compared with the standard rubber compound shown in control group 2, the modified pyrolysis carbon black prepared by the present application can significantly improve the tensile strength, hardness, tear strength and wear resistance of the rubber compound.

To sum up, the present application proposes a modified pyrolysis carbon black and a preparation method thereof. The preparation method has the characteristics of simple operation, short time consumption and controllable cost. The modified pyrolysis carbon black prepared by this method is It has the characteristics of ideal mechanical properties such as tensile strength, hardness, tear strength and wear resistance. Therefore, the modified pyrolysis carbon black and its preparation method provided by the present application have broad application prospects in the manufacture and application of pyrolysis carbon black.

The described embodiments are only to describe the preferred embodiments of the present application, and do not limit the scope of the present application. On the premise of not departing from the design spirit of the present application, various modifications made by those of ordinary skill in the art to the technical solutions of the present application and improvements, shall fall within the scope of protection determined by the claims of this application.

Claims

A preparation method of modified pyrolysis carbon black, wherein, comprising the steps:

Crushing treatment: waste tires are first crushed to obtain rubber strips, and the rubber strips are then subjected to second-stage crushing treatment to obtain rubber blocks;

Magnetic separation treatment: the rubber block is subjected to magnetic separation treatment to remove the steel wire in the rubber block to obtain the rubber block after magnetic separation treatment;

Pyrolysis and carbonization treatment: transferring the magnetically-separated rubber block to a cracking device for cracking and carbonization treatment to obtain cracked carbon residue; and

Grinding modification treatment: according to the proportion of parts by weight, firstly mix and stir the pyrolysis carbon residue and the coupling agent to obtain a mixture, and then add the mixture, stearic acid, reinforcing resin and dispersant into the grinding machine for Grinding and modifying treatment to obtain the modified pyrolysis carbon black;

Among them, in parts by weight, 100 parts of pyrolysis carbon residue; 1-5 parts of stearic acid; 0.1-5 parts of reinforcing resin; 0.1-5 parts of coupling agent; and 0.1-5 parts of dispersant.
The modified pyrolysis carbon black according to claim 1, wherein the reinforcing resin is selected from at least one of the following group: UPE resin, 203 resin, 206 resin, and high styrene resin; the coupling agent is selected from the following At least one of the group: Si69 coupling agent, Si75 coupling agent, and B69 coupling agent; the dispersant is selected from at least one of the following group: FNS-78T dispersant, BYK-ATU dispersant, and 4170 dispersant.
The method for preparing modified pyrolysis carbon black according to claim 1, wherein the device used for the first-stage crushing treatment is a strip crusher, and the device used for the second-stage crushing treatment is a granular crusher.
The method for preparing modified pyrolysis carbon black according to claim 1, wherein the particle size of the glue block is less than or equal to 30 mm.
The method for preparing modified pyrolysis carbon black according to any one of claims 1-4, wherein the pyrolysis carbonization treatment is specifically: pyrolysis carbonization treatment at a temperature of 400°C to 500°C.
The preparation method of modified pyrolysis carbon black according to any one of claims 1-4, wherein the pyrolysis carbon residue and the coupling agent are mixed and stirred in a mixing tank, and the stirring temperature is 120° C.-150° C. The time is 0.5-1h.
The method for preparing modified pyrolysis carbon black according to any one of claims 1-4, wherein the grinding modification treatment is specifically: grinding modification treatment at a temperature of 50°C-150°C.
A modified pyrolysis carbon black, wherein, in parts by weight, comprising:

100 parts of pyrolysis carbon residue;

1-5 parts of stearic acid;

Reinforcing resin 0.1-5 parts;

0.1-5 parts of coupling agent; and

0.1-5 parts of dispersant.
The modified pyrolysis carbon black according to claim 8, wherein, in parts by weight, it comprises: 100 parts of pyrolysis carbon residue, 4 parts of stearic acid, 2 parts of reinforcing resin, 5 parts of coupling agent and 3 parts of dispersing agent share.
The modified pyrolysis carbon black according to claim 8 or 9, wherein the reinforcing resin is selected from at least one of the following groups: UPE resin, 203 resin, 206 resin, and high styrene resin; the coupling agent is selected from At least one from the following group: Si69 coupling agent, Si75 coupling agent, and B69 coupling agent; dispersant selected from at least one of the following group: FNS-78T dispersant, BYK-ATU dispersant, and 4170 dispersant agent.