CN111662576A - Preparation method of quasi-in-situ modified pyrolytic carbon black - Google Patents
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Abstract
The invention discloses a preparation method of quasi-in-situ modified pyrolytic carbon black, which comprises the following steps: (1) pyrolyzing the waste tire to generate solid matters; (2) after the solid is cooled to room temperature, adding a modifier, and fully mixing to form a uniform mixture, wherein the adding amount of the modifier is 1.0-3.0% of the mass of the solid; (3) and carrying out superfine grinding on the mixture at the modification temperature of 50-240 ℃ to obtain a ground material, starting to pass through a separation system when the particle size of the ground material is less than or equal to 50 mu m, and finally collecting the modified pyrolytic carbon black through the separation system. The quasi-in-situ interface coating modification reduces or prevents primary particles of the pyrolytic carbon black from forming aggregate particle size, effectively inhibits further coalescence or agglomeration, further improves the dispersion and distribution homogenization of the pyrolytic carbon black in matrix glue, and increases the surface functional group of the pyrolytic carbon black so as to improve the dynamic and static physical and mechanical properties of the pyrolytic carbon black.
Description
Technical Field
The invention relates to the field of pyrolytic carbon black modification and application thereof in tires and rubber products, in particular to a preparation method of quasi-in-situ modified pyrolytic carbon black.
Background
Today, the contradiction between the environment and resources is becoming more acute. With the vigorous development of the automobile industry and the road transportation industry, the demand of tires is increasing day by day, the problem of waste tires is not ignored, and the quantity of the waste tires is increasing. The amount of waste tires in the world is huge, and the amount of waste tires that cannot be utilized rises year by year. The waste tires are also called black pollution, and if the waste tires are produced in large quantity, the tires can be accumulated in large quantity if the tires cannot be disposed in time, the tires are difficult to naturally degrade, and the ecological resources are also influenced badly. Therefore, a reasonable and effective waste tire treatment method must be found, so that the full utilization of rubber resources is ensured, the real protection of the environment is realized, and the final sustainable development of economy is achieved.
The waste tires are treated by mainly stacking and burying, original shape utilization, heat utilization and recycling. The recycling and recycling mainly comprises tire retreading, reclaimed rubber utilization, rubber powder utilization and thermal cracking treatment of waste tires. The thermal cracking method not only can thoroughly and effectively treat and recycle the waste tires, but also can obtain products with higher added values, such as pyrolysis gas, pyrolysis oil and thermal pyrolysis carbon black. After the thermal cracking of used tires, the solid product produced is mainly pyrolytic Carbon Black (CB)P) There are also some inorganic constituents (ash) and small amounts of macromolecular rubber hydrocarbons which do not decompose completely. Thus, CBPIs a mixture of carbon black and ash, and the quality and market application of the mixture restrict the economy of the pyrolysis recovery process of the waste tires. Due to CBPContains relatively much ash and has carbonaceous deposit on the surfaceAnd low activity, which greatly limits its application range, and thus to CB by a reasonably efficient methodPThe modification treatment is carried out, and the application field of the modified. At present, CBPThe modification mainly comprises the aspects of superfine grinding modification, modifier modification and acid washing modification.
Ultra-fine treated CBPThe surface activity of the (A) is improved, which is beneficial to improving the physical and mechanical properties of vulcanized rubber, but the defects are that the particle size of the carbon black is reduced, the particles are easy to agglomerate, and the dispersibility in the rubber is reduced. To better align the CBPThe application in rubber can be carried out after superfine grinding treatment to CBPChemically modifying to obtain CBPSurface activity is changed to thereby make the polymer and CBPThe polymer material is tightly combined, so that various properties of the polymer material are improved. To CBPThe main purpose of acid pickling modification is to remove ash in the acid pickling modification, but the acid pickling method is not environment-friendly and high in cost, and therefore, the applicability is not strong.
Therefore, technical personnel in the field are dedicated to developing a method for modifying the pyrolytic carbon black in situ, the technical operation is convenient, the environment is friendly, the quality index of the finished product is obviously improved, and the application field of the pyrolytic carbon black is expanded.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is how to modify pyrolytic carbon black to improve and enrich the surface functional group activity of pyrolytic carbon black, improve the compatibility and dispersibility with matrix rubber, and increase the degree of bonding between pyrolytic carbon black and rubber.
In order to achieve the aim, the invention provides a preparation method of quasi-in-situ modified pyrolytic carbon black, which comprises the following steps:
(1) pyrolyzing the waste tire to generate solid matters;
(2) after the solid is cooled to room temperature, adding a modifier, and fully mixing to form a uniform mixture, wherein the adding amount of the modifier is 1.0-3.0% of the mass of the solid;
(3) and carrying out superfine grinding on the uniform mixture at the modification temperature of 50-240 ℃ to obtain a ground material, starting to pass through a separation system when the particle size of the ground material is less than or equal to 50 mu m, and finally collecting the modified pyrolytic carbon black through the separation system.
Further, the time from the uniform mixture in the step (3) to the start of the passage through the separation system via the ultrafine pulverization is 5 seconds or more.
Further, the time from the uniform mixture in the step (3) to the start of the passage through the separation system via the micronization was 5 seconds.
Further, the modification temperature in the step (3) is 50-100 ℃ through self-friction heat generation of the crushing equipment, or the crushing equipment is externally heated by a heating medium to 100-240 ℃.
Further, the heating medium is water or oil.
Further, the modifier is polyhydroxy borate surfactant.
The invention also provides modified pyrolytic carbon black which is prepared by the preparation method of the quasi-in-situ modified pyrolytic carbon black, wherein the mass fraction of the modifier in the modified pyrolytic carbon black is 1.0-3.0%.
Further, the modifier is polyhydroxy borate surfactant.
Further, the particle size of the modified pyrolytic carbon black is in the range of 0.8-50 μm.
Further, the ash content of the modified pyrolytic carbon black is 20% or less.
The method comprises the steps of carrying out on-line superfine grinding on solid matters generated by pyrolysis of the waste tires, and simultaneously adding a modifier according to a certain proportion to carry out quasi-in-situ activation modification so as to prepare modified pyrolytic carbon black. The essence of the quasi-in-situ modification is as follows: the carbon black product is formed by a pyrolysis process on a production line, and simultaneously, activation modification is carried out simultaneously with superfine grinding, so that the particle size of a conglomerate formed by primary particles of the pyrolytic carbon black can be reduced to the maximum extent, further agglomeration is prevented more effectively, and the surface activity of the pyrolytic carbon black is increased and improved.
Compared with the prior art, the solid substance formed by pyrolysis of the waste tire is mixed with the modifier and then subjected to surface grafting coating through high-shear crushing (ultrafine crushing modes such as jet milling, grinding crushing and the like), so that the interface compatibility of the pyrolytic carbon black is improved, and the dispersibility in the matrix adhesive is improved; the surface active groups (functional groups such as hydroxyl, amino, carboxyl and the like) of the pyrolytic carbon black are increased, and the bonding degree with the matrigel is increased; the quasi-in-situ interface is coated and modified, so that the particle size of aggregates formed by primary particles of the pyrolytic carbon black is reduced or prevented, further coalescence or agglomeration is effectively restrained, the dispersion and distribution homogenization of the pyrolytic carbon black in matrix rubber are further improved, and the dynamic and static physical and mechanical properties of the pyrolytic carbon black are further improved;
the process flow of the invention is suitable for the modification of the pyrolytic carbon black on the production line, and the operation is convenient; the adopted polyhydroxy borate modifier is safe, environment-friendly and pollution-free, and is beneficial to environmental protection; the prepared modified pyrolytic carbon black can replace carbon black N660 to be applied to various large rubber fields, and the production and manufacturing cost of the fields is reduced;
the self-friction heating of the crushing equipment reaches the modification temperature of 50-100 ℃ or the external heating of the crushing equipment is carried out through the heating medium to reach the modification temperature of 100-240 ℃, and the self-friction heating mode or the external heating with water or oil is utilized, so that the energy consumption is reduced, and the energy is saved.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a strain-G' plot of the compound at 1Hz and 60 ℃ for example two of the present invention;
FIG. 2 is a strain-G' plot of 1Hz vulcanizate at 60 ℃ for example two of the present invention;
FIG. 3 is a strain Tan plot of the compound at 1Hz and 60 ℃ for example two of the present invention;
FIG. 4 is a graph of strain-Tan for 1Hz vulcanizate at 60 ℃ for example two of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
In the present application, the time mentioned in "the time from the mixture to the start of passing through the separation system via the micronization" and "the time kept in the micronization environment for 5s or 10 s" each refer to the sum of the first time for the mixture to be subjected to the micronization to obtain a pulverized material and the second time for the pulverized material to pass from the pulverizing apparatus to the separation system.
Example one
Carrying out on-line superfine grinding on solid obtained by pyrolyzing the waste tires, and simultaneously adding a borate modifier B-69 (the borate modifier B-69 is commercially available) at the same time, wherein the using amount of the borate modifier B-69 is 2% of that of the solid, the crushing temperature is 110 ℃, and the crushing temperature is kept for 5s in a superfine crushing environment, so as to obtain the modified pyrolytic carbon black. The ash content of the modified pyrolytic carbon black is less than or equal to 20 percent.
The particle size of the modified pyrolytic carbon black compared to unmodified pyrolytic carbon black is shown in tables 1-1:
TABLE 1-1 characteristic particle size of modified and unmodified pyrolytic carbon blacks
The results of the identification (standard: GB/T3780.18-2017) of the 3 modified pyrolytic carbon blacks and the N660 natural standard gum are shown in the tables 1-2:
TABLE 1-2 Natural gum Standard glue test recipe (parts by mass)
Note: boric acid ester-I, boric acid ester-II and boric acid ester-III are respectively samples taken in the front stage, the middle stage and the rear stage of the discharging of the modified pyrolytic carbon black; n660 is a product of Jiangxi black cat carbon black GmbH, and the national standard No. 1 adhesive is a product of Yunnan agricultural reclamation group LLC.
Results comparing the effect of different modified pyrolytic carbon blacks with N660 on parameters during vulcanization of natural standard gums are shown in tables 1-3:
tables 1-3 Effect of modified pyrolytic carbon blacks on vulcanization behavior parameters
Note: ) Tc10 is scorch time, Tc50 is half cure time, Tc90 is process positive cure time, ML is the lowest torque, MH is the highest torque.
Compared with N660 and unmodified pyrolytic carbon black, the boric acid ester-I pyrolytic carbon black, the boric acid ester-II pyrolytic carbon black and the boric acid ester-III pyrolytic carbon black have shortened scorching time Tc10 and process positive vulcanization time Tc90 and Tc 50. There was no significant difference in the effect on the vulcanization profile between the three modified pyrolytic carbon blacks.
The results of comparing the mechanical properties of different modified pyrolytic carbon blacks and the natural standard rubber of N660 are shown in tables 1-4:
TABLE 1-4 Effect of modified pyrolytic carbon blacks on mechanical Properties
Note: vulcanization conditions are as follows: 30min at 145 ℃.
In the embodiment, the 2% boric acid ester modified pyrolytic carbon black has obviously improved performance compared with unmodified pyrolytic carbon black; the strength of the modified pyrolytic carbon black basically reaches the level of N660 of the finished carbon black; the performance of the 2% borate modified pyrolytic carbon black sampled at three different positions is not large in fluctuation and is basically stable.
Example two
And carrying out on-line superfine grinding on solid obtained by pyrolyzing the waste tires, and simultaneously adding a boric acid ester modifier B-69 or a stearic acid modifier (the amount of the modifier is 2 percent of the amount of the solid), wherein the grinding temperature is 150 ℃, and the superfine grinding environment is kept for 5s, so as to obtain the modified pyrolytic carbon black.
The results of the composition of the modified pyrolytic carbon black in the V-belt formulation are shown in Table 2-1:
TABLE 2-1V-belt test formulation
Note: the national standard No. 1 glue is a product of Yunnan agricultural reclamation group Limited liability company and a product of N330-Jiangxi black cat carbon black share Limited company
The Mooney viscosities of 4V belt formulations in Table 2-1 were measured and the effect of different pyrolytic carbon blacks on the Mooney viscosities were compared and the results are shown in Table 2-2:
TABLE 2-2 Effect of different pyrolytic carbon blacks on Mooney viscosity
Note: ML1+4, 100 ℃, wherein M represents Mooney, L represents a large rotor, and the preheating time is 1 min; 4- -the rotation time is 4 min; 100 ℃ C- -the test temperature is 100 ℃.
As can be seen from Table 2-2, the Mooney viscosity increased when the modified pyrolytic carbon black was substituted for N660; the Mooney viscosity of the modified pyrolytic carbon black is slightly increased compared to that of the unmodified pyrolytic carbon black, and the Mooney viscosities of the two modified pyrolytic carbon blacks are equivalent.
Results comparing the effect of different modified pyrolytic carbon blacks on the parameters during vulcanization of V-belts with N660 are shown in tables 2-3:
TABLE 2-3 Effect of modified pyrolytic carbon blacks on vulcanization behavior parameters
Note: tc10 is the scorch time, Tc90 is the process positive cure time, ML is the lowest torque, MH is the highest torque.
As is clear from tables 2 to 3, the scorch time Tc10, the process cure time Tc90, and the torque of the modified pyrolytic carbon black were all comparable to those of the unmodified pyrolytic carbon black. The modified pyrolytic carbon black has extended Tc10 and shortened Tc90 compared to N660.
The mechanical properties of the V-belts of different modified pyrolytic carbon blacks and N660 are compared and shown in tables 2-4:
TABLE 2-4 Effect of modified pyrolytic carbon blacks on mechanical Properties
Note: vulcanization conditions are as follows: 151 ℃ for 15 min.
As can be seen from tables 2-4, compared with N660, the tensile strength, the tearing strength, the hardness, the stress at definite elongation, the elasticity, the flexing resistance and the compression fatigue temperature rise of the V-belt made of the pyrolytic carbon black which is not treated by the modifier and is treated by the stearic acid modifier are basically equivalent, the wear resistance is improved, and the wear volume is respectively reduced by 12.7 percent and 17.7 percent; the triangular belt made of the boric acid ester modifier pyrolytic carbon black not only has improved tensile property, but also has obviously improved yield resistance and wear resistance (the abrasion volume is reduced by 33.4%), and the analysis reason is probably that the interaction between the pyrolytic carbon black and the rubber matrix is enhanced after the boric acid ester modification.
As shown in FIGS. 1-2, the Payne effect of the pyrolytic carbon black is weakened after the modification by boric acid ester, and the dispersibility of the pyrolytic carbon black in matrix gum is improved. Under the action of variable external force, the phenomenon that the dynamic modulus of the filled rubber is sharply reduced along with the increase of strain is called Payne effect.
As shown in FIGS. 3-4, the loss factor tan is reduced after the pyrolytic carbon black is modified, the low hysteresis performance is improved, and the borate modification is obviously improved.
The pyrolytic carbon black modification of this example had essentially no effect on processability and vulcanization characteristics; the boric acid ester modified pyrolytic carbon black can obviously improve the wear resistance and the flexing resistance; the boric acid ester modified pyrolytic carbon black can improve the dispersibility of the boric acid ester modified pyrolytic carbon black in matrix glue; borate modified pyrolytic carbon black can improve low hysteresis performance; the boric acid ester has better modification effect on the pyrolytic carbon black than stearic acid; the boric acid ester modified pyrolytic carbon black equivalently replaces N660, so that the comprehensive quality of the V-belt can be improved.
EXAMPLE III
And carrying out on-line superfine grinding on a solid obtained by pyrolyzing the waste tire, and simultaneously adding boric acid ester B-69 or a silane coupling agent (the dosage of the modifier is 2 percent of that of the solid), wherein the grinding temperature is 140 ℃, and the superfine grinding environment is kept for 10s, so that the modified pyrolytic carbon black is prepared.
The all-steel sidewall rubber is shown in a table 3-1:
TABLE 3-1 all-steel sidewall rubber test formulation
Note: the national standard No. 1 glue is a product of Yunnan agricultural reclamation group Limited liability company, BR9000 is a Yanshan petrochemical product, and N375 is a product of Jiangxi black cat carbon black corporation.
Results of a comparison of the effect of different modified pyrolytic carbon blacks on Mooney viscosity are shown in tables 3-2:
3-2. Effect of different pyrolytic carbon blacks on Mooney viscosity
Note: ML1+4, 100 ℃, wherein M represents Mooney, L represents a large rotor, and the preheating time is 1 min; 4- -the rotation time is 4 min; 100 ℃ C- -the test temperature is 100 ℃.
Results comparing the effect of different modified pyrolytic carbon blacks with N660 on parameters during vulcanization of all steel sidewall rubber are shown in tables 3-3:
3-3. Effect of modified pyrolytic carbon Black on vulcanization Property parameters
Note: tc10 is the scorch time, Tc90 is the process positive cure time, ML is the lowest torque, MH is the highest torque.
As is clear from tables 3 to 3, the modified pyrolytic carbon black has a shorter scorch time Tc10 and a shorter process curing time Tc90 than N660, and the torque effect is less significant.
The mechanical property comparison results of the all-steel sidewall rubber prepared by different modified pyrolytic carbon blacks and N660 are shown in tables 3-4:
tables 3-4 Effect of modified pyrolytic carbon blacks on mechanical Properties
Note: vulcanization conditions are as follows: 151 ℃ for 20 min.
As shown in tables 3-4, after the unmodified and modified pyrolytic carbon black replaces N660, the hardness, elasticity and compression temperature rise change are not changed greatly, the stress at definite elongation is reduced slightly, the tensile strength, elongation at break and tear strength are improved, the flexing resistance of the modified pyrolytic carbon black is improved, and the improvement range of the tensile property and the flexing resistance of the borate modified pyrolytic carbon black is most obvious.
The results of comparing the effect of all-steel sidewall rubber made from different modified pyrolytic carbon blacks on thermal oxidative aging performance are shown in tables 3-5:
TABLE 3-5 Effect of all-steel sidewall rubber made from different modified pyrolytic carbon blacks on thermal oxidative aging Performance
Note: aging conditions are as follows: 100 ℃ for 72 h.
As can be seen from tables 3-5, after thermal oxidative aging at 100 ℃ for 72h, the tensile property of the unmodified pyrolytic carbon black is the worst, the aging resistance of the modified pyrolytic carbon black is superior to N660, and the thermal oxidative aging resistance of the borate modified pyrolytic carbon black is the best.
The modified pyrolytic carbon black of this example had essentially no effect on processability and vulcanization characteristics; the boric acid ester modified pyrolytic carbon black can obviously improve the flexing resistance; boric acid ester modified pyrolytic carbon black can improve thermal-oxidative aging performance; the modification effect of the borate coupling agent on the pyrolytic carbon black is better than that of a silane coupling agent; the boric acid ester modified pyrolytic carbon black equivalently replaces N660, so that the comprehensive performance of the all-steel tire side can be improved.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A preparation method of quasi-in-situ modified pyrolytic carbon black is characterized by comprising the following steps:
(1) pyrolyzing the waste tire to generate solid matters;
(2) after the solid is cooled to room temperature, adding a modifier, and fully mixing to form a uniform mixture, wherein the adding amount of the modifier is 1.0-3.0% of the mass of the solid;
(3) and carrying out superfine grinding on the uniform mixture at the modification temperature of 50-240 ℃ to obtain a ground material, starting to pass through a separation system when the particle size of the ground material is less than or equal to 50 mu m, and finally collecting the modified pyrolytic carbon black through the separation system.
2. The method for preparing quasi in situ modified pyrolytic carbon black of claim 1, wherein the time from the micronization of the homogeneous mixture to the start of the passage through the separation system in step (3) is 5 seconds or more.
3. The method for preparing quasi in situ modified pyrolytic carbon black of claim 2, wherein the time from the micronization of the homogeneous mixture to the start of the passage through the separation system in step (3) is 5 seconds.
4. The method for preparing quasi in-situ modified pyrolytic carbon black according to claim 1, wherein the modification temperature in step (3) is 50-100 ℃ by self-friction heat generation of the crushing equipment, or 100-240 ℃ by external heating of the crushing equipment through a heating medium.
5. The method of preparing quasi in situ modified pyrolytic carbon black of claim 4, wherein the heating medium is water or oil.
6. The method of preparing a quasi in situ modified pyrolytic carbon black of claim 1, wherein the modifier is a polyhydroxy borate surfactant.
7. A modified pyrolytic carbon black, characterized in that it is provided as obtained via the method for preparing quasi in-situ modified pyrolytic carbon black of claim 1, wherein the mass fraction of the modifier in the modified pyrolytic carbon black is 1.0% to 3.0%.
8. The modified pyrolytic carbon black of claim 7, wherein the modifier is a polyhydroxy borate surfactant.
9. The modified pyrolytic carbon black of claim 8, wherein the particle size of the modified pyrolytic carbon black is in the range of 0.8 to 50 μm.
10. The modified pyrolytic carbon black of claim 8, wherein the ash content of the modified pyrolytic carbon black is 20% or less.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112322076A (en) * | 2020-11-04 | 2021-02-05 | 中南大学 | Method for preparing carbon black |
| CN113583483A (en) * | 2021-08-05 | 2021-11-02 | 烟台融晟新材料有限公司 | Preparation and method of hydrophilic carbon black for papermaking industry |
| CN113999546A (en) * | 2021-10-09 | 2022-02-01 | 济南恒誉环保科技股份有限公司 | Secondary treatment process and device for cracked carbon black |
| CN115418119A (en) * | 2022-07-06 | 2022-12-02 | 新疆轮匠碳中和产业园有限公司 | Modification method and application of waste tire pyrolytic carbon black |
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| CN112322076A (en) * | 2020-11-04 | 2021-02-05 | 中南大学 | Method for preparing carbon black |
| CN112322076B (en) * | 2020-11-04 | 2021-10-01 | 中南大学 | Method for preparing carbon black |
| CN113583483A (en) * | 2021-08-05 | 2021-11-02 | 烟台融晟新材料有限公司 | Preparation and method of hydrophilic carbon black for papermaking industry |
| CN113999546A (en) * | 2021-10-09 | 2022-02-01 | 济南恒誉环保科技股份有限公司 | Secondary treatment process and device for cracked carbon black |
| CN115418119A (en) * | 2022-07-06 | 2022-12-02 | 新疆轮匠碳中和产业园有限公司 | Modification method and application of waste tire pyrolytic carbon black |
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