CN113563743B - Catalytic regeneration method of pyrolysis carbon black - Google Patents
Catalytic regeneration method of pyrolysis carbon black Download PDFInfo
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
- C09C1/565—Treatment of carbon black ; Purification comprising an oxidative treatment with oxygen, ozone or oxygenated compounds, e.g. when such treatment occurs in a region of the furnace next to the carbon black generating reaction zone
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a catalytic regeneration method of pyrolysis carbon black, which comprises the following steps: a. carrying out catalytic heating activation treatment on the cracking carbon black, wherein the catalyst is selected from at least one of ferric chloride, cobalt chloride, nickel chloride, copper sulfate and zinc chloride to obtain activated cracking carbon black; b. and c, cooling the cracked carbon black obtained in the step a to obtain the regenerated carbon black. According to the regeneration method of the pyrolysis carbon black, the metal salt catalyst is added in the activation process, so that the activation temperature can be reduced, the activation time can be shortened, the pyrolysis carbon black is activated under a milder condition, a colloidal layer on the surface of the pyrolysis carbon black is removed, the active sites are increased, the pyrolysis carbon black can be reused in rubber, and the recycling of solid waste resources is realized.
Description
Technical Field
The invention belongs to the technical field of rubber reinforcement, and particularly relates to a catalytic regeneration method of pyrolysis carbon black.
Background
The automobile industry in China is rapidly developed, the rubber tire industry is driven to grow up rapidly, but a large amount of waste tires are generated at the same time, if the waste tires are not treated timely enough, the land resources are seriously wasted, and the problems of fire, mosquito breeding, water source pollution and the like are easily caused, so that the ecological environment is worsened. At present, thermal cracking technology is the most promising way to treat waste tires, and cracked carbon black is also a product with high potential value as one of the byproducts. Because the cracked carbon black has wide particle size distribution, high ash content, poor surface activity and low structure degree, the cracked carbon black has unsatisfactory effect when being continuously used as a reinforcing material of rubber, and can only be used for low-end rubber products or used for replacing a few commercial carbon blacks at present. In order to fully realize the effective utilization of resources, the cracked carbon black needs to be further treated so as to reach the level of the commercial carbon black, and the high-value utilization of the cracked carbon black is realized.
At present, the performance of the cracking carbon black is further improved mainly from two aspects, namely, the reduction of ash content and the surface modification. The ash content in the pyrolysis carbon black is obviously much higher, generally between 17% and 19%, compared with the low ash content (less than 0.7%) of the commercial carbon black, and the presence of a large amount of ash causes a great reduction in the surface activity and the structure degree of the pyrolysis carbon black, which in turn affects the reinforcing performance thereof. Many researchers have conducted intensive research on the method, for example, the ash impurities in the cracked carbon black can be effectively removed by adopting a sulfuric acid + sodium hydroxide treatment method, the surface area of the cracked carbon black is increased, and the structure degree is improved. The surface modification aims at reducing the agglomeration phenomenon of the cracking carbon black, improving the dispersibility of the cracking carbon black, enhancing the compatibility between carbon black particles and rubber polymers and further improving the reinforcing performance of the cracking carbon black. If the surface grafting method is adopted, unsaturated long olefin chains are grafted on the surface of the cracking carbon black, the affinity between the carbon black and rubber molecules is increased, the reinforcing efficiency is improved, and if the plasma modification is adopted, the surface energy of the cracking carbon black is improved within a short time by using different types of plasmas, so that the surface energy of the cracking carbon black is similar to the surface energy of the substrate rubber, namely the interaction between the cracking carbon black and the rubber substrate is improved, and meanwhile, the internal structure of the cracking carbon black is basically unchanged.
The further deep processing treatment of the cracked carbon black can greatly improve the practical application value of the cracked carbon black, so that the quality of the cracked carbon black is close to the standard of commercial carbon black, and the effective reutilization of waste resources is promoted while the great economic value is generated.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: the cracking carbon black has a higher ash content in the aspect of components, and a colloidal layer is arranged on the surface of the cracking carbon black and is left for rubber cracking, so that the existence of the colloidal layer prevents the surface of the cracking carbon black from directly interacting with a new rubber substrate, and the reinforcing performance of the cracking carbon black is greatly reduced. Therefore, on the premise of not changing the internal structure of the cracked carbon black, the removal of other impurities except the carbon black, including the colloidal layer on the surface of the cracked carbon black, is a key point for effectively improving the reinforcing activity of the cracked carbon black. Therefore, it is urgently needed to develop a regeneration method of the pyrolysis carbon black, which removes ash and colloidal layers of the pyrolysis carbon black at low cost, recovers the original activity of the pyrolysis carbon black, and improves the additional value of the pyrolysis carbon black.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a catalytic regeneration method of the pyrolysis carbon black, so that the internal structure of the pyrolysis carbon black cannot be rearranged, the colloidal layer adsorbed on the surface of the pyrolysis carbon black can be effectively removed, the activity of the pyrolysis carbon black is fully recovered, the obtained regeneration carbon black has better reinforcing performance, and the prepared regeneration carbon black can be reused in rubber, so that the cyclic reuse of solid waste resources is realized.
The catalytic regeneration method of the pyrolysis carbon black comprises the following steps:
a. carrying out catalytic heating activation treatment on the cracking carbon black, wherein the catalyst is selected from at least one of ferric chloride, cobalt chloride, nickel chloride, copper sulfate and zinc chloride to obtain activated cracking carbon black;
b. and c, cooling the cracked carbon black obtained in the step a to obtain the regenerated carbon black.
According to the advantages and technical effects of the catalytic regeneration method of the pyrolysis carbon black, 1, in the method of the embodiment of the invention, metal salt catalysts such as ferric chloride, cobalt chloride, nickel chloride, copper sulfate, zinc chloride and the like are added in the activation process, covalent bonds such as carbon-oxygen, carbon-carbon and the like in a colloidal layer on the surface of the pyrolysis carbon black can be coupled with a d-vacant orbit of a transition metal, so that the bond energy is reduced, the further decomposition of the colloidal layer is promoted, the activation efficiency is improved, the activation temperature is reduced, the activation time is shortened, the pyrolysis carbon black can be activated under a milder condition, and the activity of the carbon black is effectively recovered; 2. in the method of the embodiment of the invention, the pyrolysis carbon black subjected to heating and activating treatment is cooled, and the added catalyst can activate the pyrolysis carbon black at medium and low temperature, and the cooling treatment can adopt rapid cooling or natural cooling, because the internal structure of the carbon black is not easy to change when the lower activation temperature is adopted, the pyrolysis carbon black subjected to heating and activating treatment can be prevented from graphitizing, thereby finally improving the 300% definite elongation of the regenerated carbon black; 3. in the method of the embodiment of the invention, the reinforcing performance of the regenerated carbon black is obviously improved, and the regenerated carbon black can be used as a substitute of commercial carbon black, so that the production cost of rubber is reduced; 4. the method provided by the embodiment of the invention realizes recycling of solid waste resources, is simple in operation method, has low requirements on equipment, is beneficial to large-scale production, and has wide application prospects.
In some embodiments, the catalyst is present in an amount of 0.1 to 5% by mass of the cracked carbon black.
In some embodiments, in the step a, the activation temperature is 300-; and/or in the step b, the cooling speed is 10-1000 ℃ min-1And cooling to 0-450 deg.c.
In some embodiments, the step a, the activation treatment is performed under vacuum conditions with an absolute pressure of 104-102Pa。
In some embodiments, in step a, the activation treatment is an oxidizing atmosphere, the oxidizing gas is at least one selected from oxygen, carbon dioxide, chlorine, water vapor or air, and the gas flow rate is controlled to be 0.01-0.5L · s-1。
In some embodiments, in the step a, the activation temperature is 300-; and/or in the step b, the cooling mode is to spray water mist to the cracked carbon black.
In some embodiments, in step a, the cracked carbon black is treated with an acid solution before the activation treatment, and then subjected to a milling treatment.
In some embodiments, the acid solution is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, hydrofluoric acid, fluorosilicic acid, methanesulfonic acid, ethanesulfonic acid, and perchloric acid; and/or the acid concentration is 2-5 mol.L-1The acid liquid treatment temperature is 40-60 ℃, the acid liquid treatment time is 1-6h, the mass ratio of the volume of the acid liquid to the cracked carbon black is 6-15mL/g, and the stirring speed is 400-; and/or the particle size of the milled cracked carbon black is not larger than 320 meshes.
The embodiment of the invention also provides regenerated carbon black obtained by adopting the catalytic regeneration method of the cracking carbon black. The regenerated carbon black provided by the embodiment of the invention has the 300% definite elongation of more than 10MPa, is greatly improved compared with cracked carbon black, can be used for reinforcing rubber by completely or partially replacing commercial carbon black, and obviously reduces the production cost of rubber enterprises.
The embodiment of the invention also provides application of the regenerated carbon black in rubber. The embodiment of the invention applies the regenerated carbon black to rubber reinforcement, can completely or partially replace commercial carbon black, realizes the recycling of carbon black resources, reduces the production cost and has wide application prospect.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The catalytic regeneration method of the pyrolysis carbon black comprises the following steps:
a. carrying out catalytic heating activation treatment on the pyrolysis carbon black in a vacuum environment, wherein the catalyst is selected from at least one of ferric chloride, cobalt chloride, nickel chloride, copper sulfate and zinc chloride to obtain activated pyrolysis carbon black;
b. and c, cooling the cracked carbon black obtained in the step a to obtain the regenerated carbon black.
According to the catalytic regeneration method of the pyrolysis carbon black, disclosed by the embodiment of the invention, metal salt catalysts such as ferric chloride, cobalt chloride, nickel chloride, copper sulfate and zinc chloride are added in the activation process, and carbon-oxygen, carbon-carbon and other covalent bonds in a colloidal layer on the surface of the pyrolysis carbon black can be coupled with a d-vacant orbit of a transition metal to a certain extent, so that the bond energy is reduced, further decomposition of the colloidal layer is promoted, the activation efficiency is improved, the activation temperature is reduced, the activation time is shortened, the pyrolysis carbon black can be activated under a milder condition, and the activity of the carbon black is effectively recovered; in the method of the embodiment of the invention, the pyrolysis carbon black subjected to heating and activating treatment is cooled, and the added catalyst can activate the pyrolysis carbon black at medium and low temperature, and the cooling treatment can adopt rapid cooling or natural cooling, because the internal structure of the carbon black is not easy to change when the lower activation temperature is adopted, the pyrolysis carbon black subjected to heating and activating treatment can be prevented from graphitizing, thereby finally improving the 300% definite elongation of the regenerated carbon black; in the method of the embodiment of the invention, the reinforcing performance of the regenerated carbon black is obviously improved, and the regenerated carbon black can be used as a substitute of commercial carbon black, so that the production cost of rubber is reduced; the method provided by the embodiment of the invention realizes recycling of solid waste resources, is simple in operation method, has low requirements on equipment, is beneficial to large-scale production, and has wide application prospects.
In some embodiments, the catalyst is present in an amount of 0.1 to 5% by mass of the cracked carbon black. In the embodiment of the invention, the metal salt catalyst is added in the activation process of the cracking carbon black, so that the activation speed can be effectively accelerated, the activation temperature can be reduced by adopting a small amount of catalyst, the activation time is shortened, the activation treatment can be carried out under a milder condition, the requirement on equipment is reduced, and the service life of the equipment is prolonged.
In some embodiments, in the step a, the equipment for performing the activation treatment is not particularly limited, and any equipment capable of providing a high temperature environment, such as a muffle furnace, an ash furnace, an atmosphere furnace, or a steel belt furnace, may be preferably used. The activation temperature is 300-930 ℃, the activation time is 0.1-200min, preferably, the activation temperature is 300-500 ℃, and the activation time is 60-200 min. In the embodiment of the invention, the activation temperature and the activation time are optimized, the activation temperature and the activation time of the cracking carbon black can be effectively reduced under the action of the catalyst, more active sites are exposed on the surface of the cracking carbon black, excessive graphitization of the cracking carbon black is effectively avoided, and the performance of the regenerated carbon black is improved.
In some embodiments, the activation treatment is performed under vacuum conditions at an absolute pressure of 104-102Pa. In the embodiment of the invention, the vacuum environment is preferably adopted in the activation process, so that the organic macromolecules on the surface of the carbon black can be rapidly decomposed in vacuum, and compared with the normal pressure environment, the method is more favorable for cracking the colloid layer on the surface of the carbon black to remove, exposing more active sites and recovering the original activity of the carbon black.
In some embodiments, in the step a, the atmosphere of the activation treatment is not particularly limited, and an oxidizing atmosphere is preferably used, the oxidizing gas is at least one selected from oxygen, carbon dioxide, chlorine, water vapor or air, and the gas flow rate is controlled to be 0.01 to 0.5L · s-1Preferably 0.05 to 0.3L · s-1Further, the method isPreferably 0.05 to 0.2L · s-1. In the embodiment of the invention, an oxidizing atmosphere is preferably adopted, so that the 300% definite elongation of the obtained regenerated carbon black can be further improved.
In some embodiments, in the step b, the cooling method of the activated pyrolysis carbon black is not particularly limited, and the pyrolysis carbon black may be cooled rapidly or naturally, and the rapid cooling method is any cooling method capable of rapidly cooling the pyrolysis carbon black from a high temperature state to a low temperature state, and preferably the cooling speed is 10-1000 ℃ for min-1More preferably 400--1The temperature is reduced to 0-450 deg.C, preferably 20-50 deg.C. Experiments show that when the temperature of the carbon black is reduced to below 450 ℃, the carbon black atoms are difficult to generate a rapid graphitization process, so that the original amorphous structure is maintained to the maximum extent. In the embodiment of the invention, the activated cracking carbon black is subjected to rapid cooling treatment, so that the further graphitization of the activated cracking carbon black is effectively avoided, and the performance of the regenerated carbon black is improved. When the activation temperature is 300-500 ℃, natural cooling can be adopted to reduce the temperature due to lower activation temperature, so that the internal structure of the carbon black is not affected.
In some embodiments, preferably, the cooling manner is spraying water mist to the cracked carbon black. In the embodiment of the invention, a cooling mode of spraying water mist is preferably adopted, the water mist not only plays a role in quickly cooling, but also plays a sufficient role in washing and cleaning organic macromolecules on the surface of the carbon black, so that the reinforcing activity of the carbon black can be better recovered.
In some embodiments, in step a, the cracked carbon black is treated with an acid solution before the activation treatment, and then subjected to a milling treatment. Preferably, the acid solution is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, hydrofluoric acid, fluorosilicic acid, methanesulfonic acid, ethanesulfonic acid, and perchloric acid; the acid concentration is 2-5 mol.L-1The acid liquid treatment temperature is 40-60 ℃, the acid liquid treatment time is 1-6h, the mass ratio of the volume of the acid liquid to the cracked carbon black is 6-15mL/g, and the stirring speed is 400-800 rpm. The equipment for the grinding treatment in the embodiment of the present invention is not particularly limited, and a colloid mill, a sand mill,the particle size of the cracked carbon black after grinding treatment is preferably not more than 320 meshes. According to the method provided by the embodiment of the invention, the pretreatment is carried out before the activation treatment is carried out on the cracked carbon black, and the acid treatment and the grinding treatment are adopted in the pretreatment process, so that the 300% definite elongation of the regenerated carbon black is effectively improved, and the 300% definite elongation can be improved by more than 40%.
In some embodiments, the cracked carbon black of step a is obtained from the thermal cracking of scrap tires. According to the method provided by the embodiment of the invention, the pyrolysis carbon black obtained by thermal cracking of the waste tires is subjected to regeneration treatment, so that the regeneration carbon black with excellent performance is obtained, and the cyclic utilization of solid waste resources is realized.
The embodiment of the invention also provides regenerated carbon black obtained by the regeneration method of the pyrolysis carbon black. The regenerated carbon black provided by the embodiment of the invention has the 300% definite elongation of more than 10MPa, is greatly improved compared with a solid waste cracking carbon black raw material, can be used for reinforcing rubber by wholly or partially replacing commercial carbon black, and obviously reduces the production cost of rubber enterprises.
The embodiment of the invention also provides application of the regenerated carbon black in rubber. The embodiment of the invention applies the regenerated carbon black to rubber reinforcement, can completely or partially replace commercial carbon black, realizes the recycling of carbon black resources, reduces the production cost and has wide application prospect.
The present invention will be described in detail with reference to examples.
Example 1
(1) Acid liquor treatment: weighing 3kg of cracking carbon black in a 50L reaction kettle, adding 5mol L of total acidity-130L of mixed acid solution of hydrochloric acid and hydrofluoric acid, wherein the molar ratio of the hydrochloric acid to the hydrofluoric acid is 1:1, the temperature is 60 ℃, the processing time is 4h, and the stirring speed is 800 rpm;
(2) grinding treatment: after the acid liquor treatment reaction is finished, filtering, washing and drying, and then grinding by a homogenizer, wherein the grain size after grinding is 300 meshes;
(3) activation treatment: adding ferric chloride into the ground cracked carbon black, wherein the adding amount of the ferric chloride is that of cracking0.5 percent of the total mass of the carbon black, then transferring the carbon black into a nickel box, quickly placing the nickel box into an atmosphere furnace at 400 ℃, introducing oxygen, and setting the oxygen flow rate to be 0.2L s-1And adjusting the absolute pressure in the furnace to 102Pa, taking out after activating for 120 min;
(4) cooling treatment: spraying water mist on the cracked carbon black activated in the step (3) to quickly cool the cracked carbon black to room temperature, wherein the cooling speed is 400 ℃ for min-1And obtaining the regenerated carbon black.
The process parameters of the process of this example are shown in Table 1, and the performance data of the regenerated carbon black obtained are shown in Table 2.
Examples 2 to 8
The same procedure as in example 1 was repeated, except that the differences are shown in Table 1, and the properties of the regenerated carbon black obtained are shown in Table 2.
Example 9
The same procedure as in example 1, except that the cracked carbon black was not subjected to the acid treatment of the step (1), was conducted to obtain the regenerated carbon black having the property data shown in Table 2.
Example 10
The same procedure as in example 1, except that the cracked carbon black was not subjected to the milling treatment of the step (2), was conducted to obtain the regenerated carbon black having the property data shown in Table 2.
Example 11
The same procedure as in example 1, except that the cracked carbon black was not subjected to the step (1) acid treatment and the step (2) milling treatment, was conducted to obtain the regenerated carbon black having the property data shown in Table 2.
Comparative example 1
The same procedure as in example 1, except that in said step (3), no iron chloride catalyst was added, and the properties of the regenerated carbon black obtained are shown in Table 2.
Comparative example 2
The same procedure as in example 2, except that in the step (3), no zinc chloride catalyst was added, the activation time was 300min, and the properties of the regenerated carbon black obtained are shown in Table 2.
TABLE 1
TABLE 2
| 300% definite elongation (MPa) | Tensile Strength (MPa) | Elongation at Break (%) | |
| Example 1 | 14.7 | 22.5 | 503 |
| Example 2 | 13.8 | 21.9 | 525 |
| Example 3 | 14.2 | 21.6 | 491 |
| Example 4 | 14.5 | 22.4 | 511 |
| Example 5 | 13.9 | 21.0 | 507 |
| Example 6 | 14.6 | 22.6 | 500 |
| Example 7 | 15.1 | 22.6 | 515 |
| Example 8 | 15.3 | 22.1 | 501 |
| Example 9 | 10.5 | 17.8 | 426 |
| Example 10 | 11.2 | 16.9 | 417 |
| Example 11 | 10.8 | 17.5 | 422 |
| Comparative example 1 | 14.1 | 21.1 | 510 |
| Comparative example 2 | 13.2 | 22.5 | 503 |
| Cracking carbon black | 6.8 | 23.8 | 571 |
Note: the cracked carbon blacks in the table are the cracked carbon black feedstocks used in the processes of examples 1-11.
As can be seen from Table 2, the regenerated carbon blacks obtained from examples 1-11 after catalytic activation regeneration treatment have substantially improved 300% definite elongation performance compared with the raw material cracked carbon black, the 300% definite elongation reaches more than 10MPa, and the 300% definite elongation performance is improved by more than 40% compared with the solid waste cracked carbon black raw material. In particular, in the methods of examples 1 to 8, the acid treatment and the grinding treatment were performed before the catalytic activation treatment was performed on the cracked carbon black, and the properties of the regenerated carbon black obtained were greatly improved, and the 300% elongation reached more than 13.3Mpa, which reached the 300% elongation standard (13.3-16.3Mpa) of commercial grade carbon black.
Example 1 compared with comparative example 1, the 300% definite elongation and tensile strength of the regenerated carbon black are improved by performing activation treatment under the action of the catalyst of ferric chloride. Comparative example 2 compared to example 2, no zinc chloride catalyst was added and the activation time was increased to 300min, resulting in a regenerated carbon black having a 300% elongation still lower than that of example 2. In the embodiment of the invention, the catalyst is added in the activation process of the cracking carbon black, so that the cracking carbon black can be activated at medium and low temperature, the activation time is shortened, the activation process conditions are milder, the requirement on equipment is low, and the method is easy to popularize and apply on a large scale.
The results of a small-scale test using the regenerated carbon black of example 7 of the present invention in a sidewall rubber and an inner liner rubber are shown in Table 3.
TABLE 3
Note: 1. the amount of carbon black in the table indicates the amount of commercial carbon black and the regenerated carbon black obtained in example 1 added in 100 parts by weight of rubber;
2. the 300 percent definite elongation of the carbon black N330 is 15-18MPa, and the tensile strength and the elongation at break have no clear requirements.
3. The 300 percent definite elongation of the carbon black N660 is 13.3-16.3MPa, and the tensile strength and the elongation at break have no clear requirements.
The regenerated carbon black obtained by the method of the embodiment 7 is applied to actually produced sidewall rubber and inner liner rubber, and the test results in the table 3 show that the regenerated carbon black of the embodiment 7 can partially replace commercial carbon black N330 in the sidewall rubber and can partially or even completely replace N660 in the inner liner rubber, so that the application prospect is wide.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A catalytic regeneration method of pyrolysis carbon black is characterized by comprising the following steps:
a. carrying out catalytic heating activation treatment on the pyrolysis carbon black, wherein a catalyst is selected from at least one of ferric chloride, cobalt chloride, nickel chloride, copper sulfate and zinc chloride, the activation temperature is 300-;
b. and c, cooling the cracked carbon black obtained in the step a to obtain the regenerated carbon black.
2. A process for the catalytic regeneration of carbon black according to claim 1, wherein the catalyst is present in an amount of 0.1 to 5% by mass of the carbon black.
3. The process for catalytic regeneration of carbon black according to claim 1, wherein in step b, the temperature reduction rate is 10 to 1000 ℃ for min-1And cooling to 0-450 deg.c.
4. The process for the catalytic regeneration of carbon black according to claim 1, wherein in step a, the activation treatment is carried out under vacuum at an absolute pressure of 104-102Pa。
5. The process for catalytic regeneration of carbon black according to claim 1, wherein in step a, the gas flow rate is controlled to 0.01 to 0.5L-s-1。
6. The method for catalytic regeneration of cracked carbon black according to any one of claims 1 to 5, wherein in the step a, the activation temperature is 300-500 ℃ and the activation time is 60-200 min; and/or in the step b, the cooling mode is to spray water mist to the cracked carbon black.
7. The catalytic regeneration method for cracking carbon black according to claim 1, wherein said acid liquid is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, hydrofluoric acid, fluorosilicic acid, methanesulfonic acid, ethanesulfonic acid, and perchloric acid; and/or the acid solution has a concentration of 2-5 mol.L-1The acid liquid treatment temperature is 40-60 ℃, the acid liquid treatment time is 1-6h, the mass ratio of the volume of the acid liquid to the cracked carbon black is 6-15mL/g, and the stirring speed is 400-; and/or, the particle size of the cracked carbon black after grinding is not larger than 320 meshes.
8. A regenerated carbon black made by the method of any one of claims 1-7.
9. Use of the regenerated carbon black of claim 8 in rubber.
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