CN114031811A - Method for desulfurizing waste tires by using supercritical carbon dioxide - Google Patents
Method for desulfurizing waste tires by using supercritical carbon dioxide Download PDFInfo
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- CN114031811A CN114031811A CN202111482823.9A CN202111482823A CN114031811A CN 114031811 A CN114031811 A CN 114031811A CN 202111482823 A CN202111482823 A CN 202111482823A CN 114031811 A CN114031811 A CN 114031811A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000010920 waste tyre Substances 0.000 title claims abstract description 98
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 97
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 97
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 125
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- 230000035699 permeability Effects 0.000 claims abstract description 6
- 239000012429 reaction media Substances 0.000 claims abstract description 5
- 229920001971 elastomer Polymers 0.000 claims description 47
- 239000005060 rubber Substances 0.000 claims description 47
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical group C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000005520 cutting process Methods 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 26
- 238000005086 pumping Methods 0.000 claims description 26
- 238000005070 sampling Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000428 dust Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- 229960002447 thiram Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims 2
- -1 2' -dibenzoylaminobiphenyl disulfide Chemical compound 0.000 claims 1
- ZHMIOPLMFZVSHY-UHFFFAOYSA-N n-[2-[(2-benzamidophenyl)disulfanyl]phenyl]benzamide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1SSC1=CC=CC=C1NC(=O)C1=CC=CC=C1 ZHMIOPLMFZVSHY-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 8
- 230000023556 desulfurization Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 40
- 238000005336 cracking Methods 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 9
- 238000000197 pyrolysis Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004227 thermal cracking Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
A method for desulfurizing waste tires by using supercritical carbon dioxide belongs to the technical field of waste tire desulfurization. According to the invention, under the condition of specific temperature and pressure, the supercritical carbon dioxide is used as a reaction medium, the supercritical carbon dioxide has excellent solubility and permeability, and can swell the tire in the reaction process, bring the desulfurizer into the tire, and react with the main chain or the cross-linked bond in the cross-linked network structure to remove the sulfur element from the tire. The method has the advantages of simple technical process, strong process controllability and simple operation.
Description
Technical Field
The invention relates to the technical field of desulfurization of waste tires, in particular to a method for removing sulfur elements in waste tires by using supercritical carbon dioxide.
Background
With the development of economy and the prosperous automobile industry, automobiles have gone into thousands of households, and meanwhile, the yield of waste tires is increased day by day. The waste tires are high molecular polymers, and generate a cross-linked structure through vulcanization treatment, so that the waste tires are extremely high in stability, have larger treatment ratio than common solid wastes, and are difficult to degrade in a natural state for decades. Therefore, the disposal of used tires has been a major and difficult problem facing the automotive industry.
At present, three main ways are available for recycling waste tires: the prototype is converted into a new prototype, which mainly refers to the production of the used tire into the regenerated rubber powder or the retreading of the tire. However, due to the rapid development of rubber industry technology, the market competitiveness of reclaimed rubber and retreaded tires is poor due to the high-quality and low-price synthetic rubber. Meanwhile, the reclaimed rubber powder serving as a mixture of the road asphalt cannot be applied to the market due to high cost. The waste tires and other polymer wastes are incinerated to obtain energy such as electric power, steam and the like, and the waste tires can be treated to a certain extent, but the waste tires have lower resource utilization rate. From the perspective of polymer waste utilization, thermal cracking can not only recover energy, but also obtain products with higher added value. Thermal cracking is therefore generally considered to be a more efficient process scheme, mainly because it can produce hydrocarbons, carbon black and fuel gas with higher calorific value.
The main products of tyre cracking are cracking carbon black, cracking gas and cracking oil. Carbon black is a reinforcing and filling agent for rubber, and accounts for about 25-30% of the mass of the rubber. The main solid product after cracking of the tire is cracked carbon black, and a certain amount of carbonaceous deposits are deposited on the surface of the cracked carbon black during the cracking process. At present, the application of the cracking carbon black is mainly two aspects: as a rubber reinforcing filler, but the cracking carbon black has higher sulfur content, which limits the cracking carbon black to be used as a rubber reinforcing agent again; the active carbon is prepared by activating and modifying the cracking carbon black at a higher temperature through carbon dioxide or water vapor. The cracking gas is mainly a mixture of alkane and alkene, and comprises the following main components: methane, ethane, ethylene, propane, acetylene, butane, butene, and the like. The composition and yield of the cracked gas are greatly influenced by the cracking raw material, the cracking process and the temperature, and when the cracking temperature rises, hydrocarbons with larger molecular weight undergo further cracking and dehydrogenation reactions to generate small molecular gas. At present, most cracking processes obtain less pyrolysis gas, but the heat value is higher, and the pyrolysis gas can be used as fuel to provide energy for cracking waste tires. The pyrolysis oil is a mixture of paraffin, olefin and aromatic hydrocarbon, has a tan color, is relatively complex in composition and high in heat value, and is mainly used as fuel oil. However, the waste tire pyrolysis oil has the defects of deep color, high viscosity, high density and the like due to very high sulfur content, and the industrialization prospect of the waste tire pyrolysis oil is restricted. The over-high sulfur content also limits that the pyrolysis oil can not be directly used as fuel oil, and the pyrolysis oil must be further refined, such as desulfurization, vacuum distillation and the like, to improve the fuel oil characteristics and then be used as fuel oil.
The supercritical fluid technology utilizes the characteristics of high diffusivity, high permeability, high solubility and the like of substances in a supercritical state, and the substances in the supercritical state are used as reaction media to carry out physical or chemical reactions, so that the supercritical fluid technology is widely applied to the aspects of extraction separation, pharmacy, power generation, metallurgy, dyeing and the like, wherein a lot of researches are carried out on the aspect of processing high molecular polymers which are difficult to degrade by using the supercritical fluid, particularly waste tire rubber.
Based on the above, the invention aims to remove the sulfur content in the waste tire, and in order to solve the problem that the subsequent thermal cracking product of the tire is limited in application due to the over-high sulfur content, the invention removes the sulfur element in the waste tire by using the supercritical carbon dioxide, wherein the supercritical carbon dioxide has excellent solubility and permeability, can swell the tire in the reaction process, brings the desulfurizing agent into the tire, and reacts with the main chain or the cross-linking bond in the cross-linking network structure to remove the sulfur element from the tire.
Disclosure of Invention
The invention aims to provide a method for removing sulfur element in waste tires, which mainly uses supercritical carbon dioxide as a reaction medium, uses the excellent solubility and permeability of the supercritical carbon dioxide to better permeate a desulfurizing agent into the tires, selectively breaks S-S bonds in the waste tires, and carries the sulfur element out of the tires.
The invention is realized by adopting the following technical scheme:
firstly, cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire granules with the particle size of 0.55-1mm are selected;
further weighing 2g of a waste tire sample and 0.2g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
further, 2g of a waste tire sample and 0.2g of desulfurizing agent 2, 2' -dibenzoylamido diphenyl disulfide are weighed and mixed uniformly;
further, 2g of a waste tire sample and 0.2g of desulfurizing agent tetramethyl thiuram disulfide are weighed and mixed uniformly;
furthermore, 2g of waste tire sample and 0.2g of desulfurizing agent N-cyclohexyl-2-benzothiazole sulfonamide are weighed and mixed uniformly;
further, 2g of a waste tire sample and 0.1g of desulfurizing agent diphenyl disulfide are weighed and mixed uniformly;
further, 2g of a waste tire sample and 0.3g of desulfurizing agent diphenyl disulfide are weighed and mixed uniformly;
further, 2g of a waste tire sample and 0.4g of desulfurizing agent diphenyl disulfide are weighed and mixed uniformly;
further, placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
further, introducing carbon dioxide into the reaction kettle, adjusting the pressure in the reaction kettle to be 5-20MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 150-;
furthermore, diphenyl disulfide is used as a desulfurizer to carry out desulfurization treatment on the waste tires, and the reaction conditions are as follows: the reaction temperature is 150-;
furthermore, 2' -dibenzamido diphenyl disulfide is used as a desulfurizing agent to carry out desulfurization treatment on the waste tire, and the reaction conditions are as follows: the reaction temperature is 150-;
furthermore, the waste tire is desulfurized by using tetramethyl thiuram disulfide as a desulfurizing agent under the following reaction conditions: the reaction temperature is 150-;
furthermore, the waste tire is desulfurized by using N-cyclohexyl-2-benzothiazole sulfonamide as a desulfurizing agent under the following reaction conditions: the reaction temperature is 150-;
further, fully reacting for 1-5h after the reaction temperature and pressure reach a set value;
and further, sampling the gas in the reaction kettle after the reaction is finished, and relieving the pressure and reducing the temperature after the sampling is finished.
Compared with the prior art, the invention has the following advantages:
1. the carbon dioxide in a supercritical state is used as a reaction medium, the waste tire is fully swelled by utilizing the excellent solubility and permeability of the carbon dioxide, the desulfurizer is brought into the tire, and the carbon dioxide reacts with a main chain or a cross-linked bond in a cross-linked network structure to remove sulfur elements from the tire.
2. The method can remove about 30 percent of sulfur content in the waste wheel, and solves the problem that the application of the subsequent waste tire thermal cracking product is limited due to overhigh sulfur content.
3. The method has the advantages of simple technical process, strong process controllability and simple operation.
Drawings
FIG. 1 is a flow chart of a supercritical carbon dioxide reaction apparatus according to the present invention
Detailed Description
The following detailed description of the embodiments of the present invention is provided for the purpose of illustration, but not for the purpose of limiting the invention.
The following detailed description of embodiments of the present patent is, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.2g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 1h after the reaction temperature and pressure reach a set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 0.36 percent, and the removal rate of the sulfur content in the waste tires is 11.41 percent.
Example 2
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.2g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 350 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) sampling gas in the reaction kettle after the reaction is finished, and relieving pressure and cooling after the sampling is finished and the reaction is fully carried out;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 0.48 percent, and the removal rate of the sulfur content in the waste tires is 29.90 percent.
Example 3
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.2g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 3 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 0.38%, and the removal rate of the sulfur content in the waste tires is 16.91%.
Example 4
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.2g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 0.40 percent, and the removal rate of the sulfur content in the waste tires is 15.46 percent。
Example 5
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of waste tire sample and 0.1g of desulfurized diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 0.32%, and the removal rate of the sulfur content in the waste tires is 4.33%.
Example 6
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.2g of desulfurizer 2, 2' -dibenzoylamido diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 1.54 percent, and the removal rate of the sulfur content in the waste tires is 18.21 percent.
Example 7
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.2g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 300 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) for collection in reactionThe gas and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 0.49%, and the removal rate of the sulfur content in the waste tires is 19.00%.
Example 8
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.2g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to be 15MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 1.43 percent, and the removal rate of the sulfur content in the waste tires is 13.51 percent.
Example 9
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.2g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to be 20MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 1.44%, and the removal rate of the sulfur content in the waste tires is 8.06%.
Example 10
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.3g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 0.33%, and the removal rate of the sulfur content in the waste tires is 3.63%.
Example 11
A method for desulfurizing waste tires by using supercritical carbon dioxide comprises the following specific steps:
(1) cutting tread rubber from waste tires, simply cleaning the tread rubber, washing off surface dust, cutting the tread rubber into small blocks, putting the small blocks into a crusher for crushing, and sieving after crushing, wherein the tire particles with the particle size of 0.55-1mm are selected;
(2) weighing 2g of a waste tire sample and 0.4g of desulfurizing agent diphenyl disulfide, and uniformly mixing the two;
(3) placing the mixture in a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to 10MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 250 ℃, and enabling the carbon dioxide to be in a supercritical state under the temperature and pressure condition;
(5) fully reacting for 4 hours after the reaction temperature and pressure reach the set value;
(6) after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and reducing the temperature;
(7) the gas collected in the reaction and the waste tire sample treated by the supercritical carbon dioxide are characterized, and the result shows that: h in the sampled gas2The S content is 0.38%, and the removal rate of the sulfur content in the waste tires is 6.15%.
The tires prepared in examples 1 to 11 after the desulfurization treatment with supercritical carbon dioxide were characterized for desulfurization effect, and the results are shown in table 1:
TABLE 1 desulfurization Effect characterization
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for desulfurizing waste tires by using supercritical carbon dioxide is characterized in that under the condition of specific temperature and pressure, the supercritical carbon dioxide is used as a reaction medium, the tire swells by utilizing solubility and permeability to bring a desulfurizing agent into the tire, and the desulfurizing agent reacts with a main chain or a cross-linking bond in a cross-linking network structure to remove sulfur elements from the interior of the tire.
2. The method for desulfurizing waste tires by using supercritical carbon dioxide according to claim 1, wherein the desulfurizing agent is diphenyl disulfide, 2' -dibenzoylaminobiphenyl disulfide, tetramethylthiuram disulfide or N-cyclohexyl-2-benzothiazolesulfenamide.
3. The method for desulfurizing used tires by using supercritical carbon dioxide according to claim 1, characterized in that the reaction conditions are as follows: the reaction temperature is 150-.
4. The method for desulfurizing waste tires by using supercritical carbon dioxide as claimed in claim 3, wherein when diphenyl disulfide is used as desulfurizing agent, the reaction conditions are as follows: the reaction temperature is 150-.
5. The method for desulfurizing waste tires by using supercritical carbon dioxide as claimed in claim 3, wherein when 2, 2' -dibenzamidodiphenyl disulfide is used as a desulfurizing agent, the reaction conditions are as follows: the reaction temperature is 150-.
6. The method for desulfurizing waste tires by using supercritical carbon dioxide as claimed in claim 3, wherein when tetramethylthiuram disulfide is used as the desulfurizing agent, the reaction conditions are as follows: the reaction temperature is 150-.
7. The method for desulfurizing waste tires by using supercritical carbon dioxide as claimed in claim 3, wherein when N-cyclohexyl-2-benzothiazole sulfenamide is used as desulfurizing agent, the reaction conditions are as follows: the reaction temperature is 150-.
8. The method for desulfurizing waste tires by using supercritical carbon dioxide according to any one of claims 2 to 7, is characterized by comprising the following steps:
(1) cutting tread rubber from waste tires, washing off surface dust, cutting the tread rubber into small blocks, placing the small blocks into a crusher for crushing, sieving after crushing, and selecting tire particles with the particle size of 0.55-1 mm;
(2) uniformly stirring and mixing the tire particles and the desulfurizer;
(3) putting the mixture into a supercritical carbon dioxide reaction kettle, pumping out air in the reaction kettle by using a vacuum pump, and closing a pressure release valve after the air is completely discharged;
(4) then introducing carbon dioxide into the reaction kettle, adjusting the pressure in the kettle to be 5-20MPa, pumping the carbon dioxide into the reaction kettle through a pressure pump to reach a preset pressure value, simultaneously heating, setting the temperature to be 150-;
(5) fully reacting for 1-5h after the reaction temperature and pressure reach the set value;
(6) and after the reaction is finished, sampling the gas in the reaction kettle, and after the sampling is finished, releasing the pressure and cooling.
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| CN202111482823.9A CN114031811A (en) | 2021-12-07 | 2021-12-07 | Method for desulfurizing waste tires by using supercritical carbon dioxide |
| PCT/CN2021/141609 WO2023103113A1 (en) | 2021-12-07 | 2021-12-27 | Method for desulfurization of waste tire by using supercritical carbon dioxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114685846A (en) * | 2022-04-14 | 2022-07-01 | 同济大学 | Supercritical de-crosslinking pre-treated rubber powder and rubber powder modified asphalt and preparation method thereof |
| CN116854990A (en) * | 2023-06-28 | 2023-10-10 | 元谋金蓬环保科技有限公司 | Waste tire reclaimed rubber treatment process |
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| JP2000095895A (en) * | 1998-07-24 | 2000-04-04 | Toyo Tire & Rubber Co Ltd | Reclamation of vulcanized rubber |
| CN101503525A (en) * | 2009-03-11 | 2009-08-12 | 北京化工大学 | Method for desulphurization, disaggregation and regeneration of vulcanized rubber |
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| CN111745860A (en) * | 2020-06-08 | 2020-10-09 | 武汉科技大学 | Waste tire smashing and desulfurizing integrated device based on supercritical carbon dioxide jet flow and application method |
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- 2021-12-27 WO PCT/CN2021/141609 patent/WO2023103113A1/en unknown
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| JP2000095895A (en) * | 1998-07-24 | 2000-04-04 | Toyo Tire & Rubber Co Ltd | Reclamation of vulcanized rubber |
| CN101503525A (en) * | 2009-03-11 | 2009-08-12 | 北京化工大学 | Method for desulphurization, disaggregation and regeneration of vulcanized rubber |
| CN104387611A (en) * | 2014-11-28 | 2015-03-04 | 天津海泰环保科技发展有限公司 | Environment-friendly method for regenerating waste rubber |
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| CN114685846A (en) * | 2022-04-14 | 2022-07-01 | 同济大学 | Supercritical de-crosslinking pre-treated rubber powder and rubber powder modified asphalt and preparation method thereof |
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| CN116854990A (en) * | 2023-06-28 | 2023-10-10 | 元谋金蓬环保科技有限公司 | Waste tire reclaimed rubber treatment process |
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| WO2023103113A1 (en) | 2023-06-15 |
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