CN114106592A - High-temperature plasma purification treatment method for waste tire pyrolysis carbon black - Google Patents
High-temperature plasma purification treatment method for waste tire pyrolysis carbon black Download PDFInfo
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- CN114106592A CN114106592A CN202111307806.1A CN202111307806A CN114106592A CN 114106592 A CN114106592 A CN 114106592A CN 202111307806 A CN202111307806 A CN 202111307806A CN 114106592 A CN114106592 A CN 114106592A
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- 239000006229 carbon black Substances 0.000 title claims abstract description 86
- 238000011282 treatment Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000746 purification Methods 0.000 title claims abstract description 27
- 239000010920 waste tyre Substances 0.000 title claims abstract description 27
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 21
- 238000005336 cracking Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000013067 intermediate product Substances 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000005087 graphitization Methods 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- -1 freon Chemical compound 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
- C09C1/482—Preparation from used rubber products, e.g. tyres
Abstract
The invention relates to a high-temperature plasma purification treatment method for waste tire pyrolysis carbon black, which comprises the following steps: cracking waste tires to obtain a cracking carbon black raw material; the cracking carbon black raw material enters a pretreatment system, and a cracking carbon black intermediate product is generated through pretreatment; the cracking carbon black intermediate product enters a high-temperature plasma purification reactor, and is subjected to purification reaction under the action of high-temperature and high-activity plasma torch gas generated by a plasma generator to obtain a high-purity carbon black raw material; and (3) allowing the high-purity carbon black raw material to enter a post-treatment modification system to finally obtain a high-purity carbon black derivative product. The method fully utilizes the characteristics of high plasma temperature, high energy density, controllable atmosphere, rich active components and the like, and makes inorganic ash in the cracking carbon black react faster and removed more thoroughly through full gas-solid phase reaction, so as to obtain a high-purity carbon black raw material, and solve the problems of environmental pollution and resource waste caused by high ash content and incapability of high-value utilization of the conventional waste tire cracking carbon black.
Description
Technical Field
The invention relates to the technical field of carbon black preparation, in particular to a high-temperature plasma purification treatment method for waste tire pyrolysis carbon black.
Background
Currently, the development of circular economy is a necessary choice for realizing the benign development of economic society, and the promotion of green development is a necessary way for eliminating and reducing the emission of pollutants. The incineration rate of the waste tires and the cracked carbon black in China is close to 55 percent. Compared with other disposal techniques, pyrolysis techniques have maximized the immobilization of carbon elements in the cracked carbon black product. However, the cracked carbon black has low quality and high impurity content, cannot be used with high value, and can only be incinerated as fuel finally. The deep resource treatment system for the waste tire cracking carbon black is an effective way for carrying out high-value resource utilization and harmless treatment on the solid wastes, and is used for developing circular economy, saving carbon black resources, reducing energy consumption, protecting ecological environment, reducing and gradually eliminating black pollution and promoting green sustainable development of rubber industry.
The ash content in the cracking carbon black mainly comprises ZnO and SiO2、Al2O3And inorganic oxides such as CaO and the like are generally purified by an acid pickling process or an acid pickling and alkali washing combined process, and the acid pickling process and the alkali washing combined process can generate high-concentration acid-base waste liquid in the production and operation processes, so that the occupied area is large, the environment is seriously polluted, the automation degree is low, and the working environment is severe. Aiming at key links in the deep resource treatment process of the waste tire cracking carbon black, the invention mainly improves the defects of low quality and high impurity content of the cracking carbon black and solves the problems of difficult marketing and incapability of recycling high-value resources.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a high-temperature plasma purification treatment method for waste tire pyrolysis carbon black, which can enable inorganic ash in the pyrolysis carbon black to react faster and be removed more thoroughly.
The invention is realized by the following technical scheme:
a high-temperature plasma purification treatment method for waste tire pyrolysis carbon black is characterized by comprising the following steps: a. cracking waste tires to obtain a cracking carbon black raw material; b. the cracking carbon black raw material enters a pretreatment system and is pretreated to generate a cracking carbon black intermediate product; c. the cracking carbon black intermediate product enters a high-temperature plasma purification reactor, and is subjected to purification reaction under the action of high-temperature and high-activity plasma torch gas generated by a plasma generator to obtain a high-purity carbon black raw material; and d, allowing the high-purity carbon black raw material to enter a post-treatment modification system to finally obtain a high-purity carbon black derivative product.
According to the technical scheme, the cracking temperature in the step a is preferably 300-.
According to the technical scheme, preferably, the pretreatment system comprises one or more of high-temperature carbonization pretreatment, crushing and grading pretreatment, screening pretreatment, acid washing and ultrasonic pretreatment and filtering and drying pretreatment.
According to the technical scheme, the high-temperature carbonization pretreatment temperature is preferably 800-1500 ℃.
According to the technical scheme, preferably, the particle size of the cracking carbon black intermediate product is 0.5-200 μm, the content of organic volatile components is 0-2%, and the content of ash is 1% -15%.
According to the technical scheme, the purification reaction temperature in the step c is preferably 1500-.
According to the above technical solution, preferably, the plasma torch gas includes one or more of argon, nitrogen, helium, carbon tetrafluoride, tetrafluoroethylene, freon, and hydrogen.
According to the above technical solution, preferably, the working gas pressure of the plasma torch gas generated by the plasma generator in the step c is 0.4-1.6Mpa, the power of the plasma generator is 50-300KW, and the flow rate of the cooling water is 10-20m3And h, the average gas temperature of the plasma torch is 5000-.
According to the above technical solution, preferably, the post-treatment modification system includes one or more of graphitization post-treatment, surface coating modification post-treatment, medicament activation post-treatment, washing, filtering and drying post-treatment.
The invention has the beneficial effects that:
the method has the advantages of simple process flow, low operation cost, continuous production realization, full utilization of the characteristics of high plasma temperature, high energy density, controllable atmosphere, rich active components and the like, and full reaction of gas and solid phases, so that inorganic ash in the cracked carbon black can be reacted more quickly and removed more thoroughly, a high-purity carbon black raw material is obtained, and the problems of environmental pollution and resource waste caused by high ash content and incapability of high-value utilization of the cracked carbon black of the conventional waste tire are solved.
Drawings
FIG. 1 is a schematic process flow diagram of example 1 of the present invention.
FIG. 2 is a schematic process flow diagram of example 2 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in the figure, the invention comprises the following steps:
a. cracking the waste tire at 800 ℃ under 300-;
b. the cracking carbon black raw material enters a pretreatment system, and is pretreated at the temperature of 800-1500 ℃ to generate a cracking carbon black intermediate product, wherein the particle size of the cracking carbon black intermediate product is 0.5-200 mu m, the content of organic volatile components is 0-2%, and the content of ash is 1-15%, and the pretreatment system in the embodiment comprises the following methods: high-temperature carbonization pretreatment, crushing and grading pretreatment, screening pretreatment, acid washing ultrasonic pretreatment, filtering and drying intervention treatment and the like;
c. the cracking carbon black intermediate product enters a high-temperature plasma purification reactor to carry out purification reaction under the action of high-temperature and high-activity plasma torch gas generated by a plasma generator, the working gas pressure of the plasma torch gas generated by the plasma generator in the embodiment is 0.4-1.6Mpa, the power of the plasma generator is 50-300KW, and the cooling water flow is 10-20m3The average temperature of the gas of the plasma torch is 5000-10000 ℃, the gas of the plasma torch comprises one or more of argon, nitrogen, helium, carbon tetrafluoride, tetrafluoroethylene, Freon and hydrogen, wherein the purification reaction temperature is preferably 1500-3500 ℃, and the purification reaction temperature is increased by high temperatureChanging the chemical composition and phase state of ash contained in the pyrolysis carbon black at a temperature to change the ash contained in the intermediate product of the pyrolysis carbon black into a gas state and discharging the gas state out of the reactor along with the high-temperature plasma tail gas, and finally obtaining a high-purity carbon black raw material;
d. the high-purity carbon black raw material enters a post-treatment modification system, wherein the post-treatment modification system comprises one or more of graphitization post-treatment, surface coating modification post-treatment, medicament activation post-treatment, washing, filtering and drying post-treatment, and the high-purity carbon black raw material is subjected to modification treatment according to different carbon black application requirements, so that a high-purity carbon black derivative product is finally obtained.
The method has the advantages of simple process flow, low operation cost, continuous production realization, full utilization of the characteristics of high plasma temperature, high energy density, controllable atmosphere, rich active components and the like, and full reaction of gas and solid phases, so that inorganic ash in the cracked carbon black can be reacted more quickly and removed more thoroughly, a high-purity carbon black raw material is obtained, and the problems of environmental pollution and resource waste caused by high ash content and incapability of high-value utilization of the cracked carbon black of the conventional waste tire are solved.
Based on the above embodiments, the present invention may be preferably selected from the following two examples:
example 1
S1, performing cracking treatment on the waste tire at 800 ℃ under 300 ℃ and 15 ℃ to obtain a cracking carbon black raw material, wherein the ash content of the cracking carbon black raw material is 15%, the organic volatile matter content is 3%, and the particle size is 0.5-10 mm;
s2, carrying out high-temperature carbonization pretreatment on the pyrolysis carbon black obtained after the waste tire is subjected to pyrolysis treatment under the protection of argon, wherein the carbonization temperature is 800-;
s3, feeding the low-volatile matter pyrolysis carbon black raw material processed in the step S2 into a crushing and grading pretreatment system, crushing the raw material by an airflow superfine crusher, and grading and screening the crushed raw material to obtain a pyrolysis carbon black intermediate product with the particle size of 10-50 mu m;
s4, feeding the cracking carbon black intermediate product into a high-temperature plasma purification reactor, wherein the working gas of the plasma is argon,the enhanced auxiliary reaction gas is carbon tetrafluoride, and the flow rate of argon is 10-20Nm3Per hour, carbon tetrafluoride flow rate is 2-5Nm3H, the average gas temperature of the high-activity ionized plasma torch is 5000-;
s5, feeding the high-purity carbon black raw material into a high-temperature graphitization post-treatment system, wherein the graphitization post-treatment temperature is 2800-.
The purity of the high-purity graphite powder product treated by the procedures is 99.9-99.99%, the particle size is 10-50 mu m, the graphitization degree is 80-90%, and the high-purity graphite powder product can replace a natural graphite raw material, so that high-value resource recycling of the cracking carbon black is realized.
Example 2
S1, performing cracking treatment on the waste tire at 800 ℃ under 300 ℃ and 15 ℃ to obtain a cracking carbon black raw material, wherein the ash content of the cracking carbon black raw material is 15%, the organic volatile matter content is 3%, and the particle size is 0.5-10 mm;
s2, carrying out high-temperature carbonization pretreatment on the pyrolysis carbon black obtained after the waste tire is subjected to pyrolysis treatment under the protection of argon, wherein the carbonization temperature is 800-;
s3, feeding the low-volatile matter pyrolysis carbon black raw material processed in the step S2 into a crushing and grading pretreatment system, crushing the raw material by an airflow superfine crusher, and grading and screening the crushed raw material to obtain a pyrolysis carbon black intermediate product with the particle size of 10-50 mu m;
s4, feeding the intermediate product of the cracked carbon black into a high-temperature plasma purification reactor, wherein the working gas of the plasma is argon, the enhanced auxiliary reaction gas is carbon tetrafluoride, and the flow of the argon is 10-20Nm3Per hour, carbon tetrafluoride flow rate is 2-5Nm3H, the average gas temperature of the high-activity ionized plasma torch is 5000-;
s5, feeding the high-purity carbon black raw material into a surface coating modification post-treatment system, wherein KOH activation treatment is adopted for surface modification, the weight ratio of carbon to KOH is 1:1-1:5, the sintering temperature is 500 ℃, and the retention time is 2 hours, so as to obtain an activated carbon black intermediate product;
s6, feeding the activated carbon black intermediate product into a washing, filtering and drying post-treatment system, wherein the weight ratio of carbon to water is 1:10, the washing times are 2-3 times, filtering out water to obtain high-purity activated carbon black with the water content of 30-50%, drying the activated carbon black at 110 ℃ until the water content is 0.5-2%, and finally obtaining the high-purity carbon black product.
The purity of the high-purity carbon black product treated by the procedures is 99.9-99.99 percent, and the specific surface area is 200m2/g-800m2And/g, the high-purity carbon black product has higher specific surface area and adsorption activity and can replace commercial carbon black, so that high-value resource recycling of the cracking carbon black is realized.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A high-temperature plasma purification treatment method for waste tire pyrolysis carbon black is characterized by comprising the following steps: a. cracking waste tires to obtain a cracking carbon black raw material; b. the cracking carbon black raw material enters a pretreatment system and is pretreated to generate a cracking carbon black intermediate product; c. the cracking carbon black intermediate product enters a high-temperature plasma purification reactor, and is subjected to purification reaction under the action of high-temperature and high-activity plasma torch gas generated by a plasma generator to obtain a high-purity carbon black raw material; d. and (3) allowing the high-purity carbon black raw material to enter a post-treatment modification system to finally obtain a high-purity carbon black derivative product.
2. The method as claimed in claim 1, wherein the cracking temperature in step a is 300-800 ℃.
3. The high-temperature plasma purification treatment method for carbon black produced by cracking waste tires according to claim 2, characterized in that the pretreatment system comprises one or more of high-temperature carbonization pretreatment, pulverization and classification pretreatment, screening pretreatment, acid washing and ultrasonic pretreatment, and filtering and drying pretreatment.
4. The method as claimed in claim 3, wherein the pretreatment temperature for high temperature carbonization is 800-1500 ℃.
5. The high-temperature plasma purification treatment method for waste tire pyrolysis carbon black as claimed in claim 1, wherein the particle size of the pyrolysis carbon black intermediate product is 0.5-200 μm, the content of organic volatile matter is 0-2%, and the content of ash is 1% -15%.
6. The method for high-temperature plasma purification treatment of carbon black from waste tires as claimed in claim 1, wherein the purification reaction temperature in step c is 1500-.
7. The high-temperature plasma purification treatment method for carbon black generated by cracking waste tires according to claim 6, wherein the gas generated by the plasma torch comprises one or more of argon, nitrogen, helium, carbon tetrafluoride, tetrafluoroethylene, freon and hydrogen.
8. The high-temperature plasma purification treatment method for carbon black from waste tire cracking as claimed in claim 7, wherein the working gas pressure of the plasma torch gas generated by the plasma generator in the step c is 0.4-1.6Mpa, the power of the plasma generator is 50-300KW, and the cooling water flow is 10-20m3And h, the average gas temperature of the plasma torch is 5000-.
9. The method for high-temperature plasma purification treatment of carbon black from waste tires according to claim 1, wherein the post-treatment modification system comprises one or more of graphitization post-treatment, surface coating modification post-treatment, chemical activation post-treatment, washing, filtering and drying post-treatment.
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Cited By (1)
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| CN114823171A (en) * | 2022-05-27 | 2022-07-29 | 昆明理工大学 | Nitrogen-oxygen doped carbon nanohorn and preparation method and application thereof |
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Application publication date: 20220301 |