CN114031636A - Mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method - Google Patents
Mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C21/00—Disintegrating plant with or without drying of the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C2201/00—Codes relating to disintegrating devices adapted for specific materials
- B02C2201/06—Codes relating to disintegrating devices adapted for specific materials for garbage, waste or sewage
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a waste silicon rubber thermal cracking recovery method assisted by mechanochemical grinding, which comprises the steps of stripping waste silicon rubber from waste silicon rubber products, crushing the waste silicon rubber into colloidal particles with the diameter of 0.1-5.0 cm by a wet crusher, centrifugally drying, compounding the colloidal particles with a catalyst, feeding the colloidal particles into a solid phase shearing grinder for mechanochemical grinding to obtain catalyst-containing superfine rubber powder, and finally feeding the colloidal particles into a pyrolysis furnace for thermal cracking to obtain recovered monomers. The catalyst is one of alkali and solid super acid, and the particle size of the catalyst is 100-500 meshes. The method can solve the problem that the waste silicon rubber is difficult to degrade into monomers for recycling, effectively combines a physical crushing recycling method and a chemical catalytic cracking recycling method of the waste silicon rubber, is pollution-free, convenient, effective, centralized in recycling of the monomers, short in cracking time, easy for subsequent collection and recycling of the monomers, and has environmental, economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of preparing high-performance materials by recycling resources, and particularly relates to a mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method.
Background
The silicon rubber is used as a synthetic rubber, and the structure of the synthetic rubber takes a silicon-oxygen bond as a main chain, so that the synthetic rubber has the characteristics of high and low temperature resistance, ozone aging resistance, high voltage resistance, radiation resistance, high air permeability, physiological inertia and the like, and has extremely wide application fields. With the increasing consumption of silicon rubber products in China, the amount of the generated waste silicon rubber is increased year by year, but the silicon rubber has extremely stable physical and chemical properties and is difficult to naturally degrade in the environment. The waste silicon rubber is generated and accumulated, so that not only is the resource waste caused, but also a large amount of space is occupied, the environment is polluted and the like. And the silicon rubber has high added value of resources, and has important economic value for recycling. Therefore, the regeneration and resource utilization of the waste silicon rubber are beneficial to the sustainable development of the composite insulator industry, and have important environmental, economic and social benefits.
The existing methods for recycling silicone rubber include physical breaking and chemical cracking. The physical crushing method is to physically crush waste silicon rubber by a shearing machine, a double-roller machine, a grinder and other equipment, and directly use the crushed waste silicon rubber as a filler after grading and screening or use the crushed waste silicon rubber after modification treatment. The physical crushing method has low requirement on equipment, simple process, no toxicity and no pollution, can realize the regeneration of the silicon rubber in a short time by only selecting reasonable regeneration process and processing aid, and is suitable for the direct utilization of silicon rubber leftover materials. But the application range is limited, and the repeated recycling of the silicon rubber can not be realized, namely the sustainable development property is not realized.
The chemical cracking method comprises a high-temperature cracking method or a catalytic (acid, alkali, salt and the like) cracking method, so that the silicon-oxygen main chain of the silicon rubber is cracked, the cracking products are dimethyl cyclosiloxane mixture (DMC) and micromolecule chain polysiloxane, and the monomers can be reused for preparing some value-added products. The high temperature cracking process requires relatively high temperature, generally greater than 300 deg.c, high power consumption and messy product variety. The yield of the monomer in the products of the alkali catalytic cracking method is low, and although some specific solvents can be added for improvement, new pollution is brought. The prior art of the acid catalytic cracking method is mature, the yield is high, but the method has serious corrosion to processing equipment, low utilization rate, difficult treatment of waste acid, reaction with fillers in silicon rubber and limited application range.
Based on the technical background, the invention provides a method for recovering silicon rubber by combining a physical crushing recovery method with a chemical catalytic cracking recovery method, wherein the stable structure of the silicon rubber is damaged to a certain extent by physical crushing, the dispersion of a catalytic system is promoted, and the reaction sites with chemical reagents are improved, so that the recovery efficiency is improved.
Disclosure of Invention
Aiming at the problems of the prior art, the invention aims to solve the problems of low recovery efficiency, high energy consumption and the like of the existing waste silicon rubber, and provides a method for assisting the thermal cracking recovery of the waste silicon rubber based on mechanical force chemical grinding.
In order to achieve the purpose, the invention adopts the following scheme:
a mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method is characterized by comprising the following steps:
A. separating waste silicon rubber from waste silicon rubber products, and crushing the separated waste silicon rubber into colloidal particles with the diameter of 0.1-5.0 cm by using a wet crusher;
B. centrifugally spin-drying the crushed colloidal particles, putting the dried colloidal particles into a solid-phase shearing grinder for mechanochemical grinding, wherein the equipment pressure is 1-10 MPa, the rotating speed is 80-200 r/min, and the grinding times are 1-5 times to obtain superfine colloidal powder;
C. compounding the superfine rubber powder with a catalyst, and then carrying out mechanochemical grinding, wherein the dosage of the catalyst is 5-8 wt%, so as to obtain the catalyst-containing superfine rubber powder;
D. and transferring the catalyst-containing superfine rubber powder into a pyrolysis furnace for thermal cracking under the condition of nitrogen atmosphere at 180 ℃ and 220 ℃ for 3 hours to obtain a recovered monomer.
The mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method is characterized by verifying the effective auxiliary effect of mechanical force grinding and the combination of mechanical force grinding and chemical catalysis on silicon rubber thermal cracking.
The water content of the wet crusher is 50% -80%, the crushing blade is a claw knife type blade and is formed by combining a movable knife and a fixed knife, and the diameter of a screen is 0.1-5.0 cm.
The water content of the rubber particles after centrifugal drying is less than or equal to 3 percent.
The solid phase shearing grinder is a millstone type mechanochemical grinder.
The catalyst adopts a chemical catalyst, and the chemical catalyst is selected from one of alkali and solid super acid.
The method comprises the following specific steps of compounding the crushed colloidal particles with a catalyst and then carrying out mechanochemical grinding: the method for obtaining the catalyst-containing superfine rubber powder is that the catalyst and crushed silicon rubber particles are evenly compounded and then put into a grinder for grinding together.
Specifically, the invention adopts the following technical scheme:
1. a method for assisting thermal cracking of waste silicon rubber by mechanical force chemical grinding is characterized by comprising the following operation processes:
A. separating waste silicon rubber from waste silicon rubber products, and crushing the separated silicon rubber into colloidal particles with the diameter of about 0.1-5.0 cm by using a wet crusher;
B. centrifugally spin-drying the crushed colloidal particles, putting the dried colloidal particles into a solid-phase shearing grinder for mechanochemical grinding, wherein the equipment pressure is 1-10 MPa, the rotating speed is 80-200 r/min, and the grinding times are 1-5 times to obtain superfine colloidal powder;
C. compounding the superfine rubber powder with a catalyst, and then carrying out mechanochemical grinding, wherein the dosage of the catalyst is 5-8 wt%, so as to obtain the catalyst-containing superfine rubber powder;
D. and transferring the superfine rubber powder into a pyrolysis furnace for thermal cracking, wherein the thermal cracking condition is 180 ℃ and 220 ℃ in a nitrogen atmosphere for 3 hours, and obtaining a recovered monomer.
2. The water content of the wet crusher is 50% -80%, the crushing blade is a claw knife type blade and is formed by combining a movable knife and a fixed knife, and the diameter of a screen is 0.1-5.0 cm.
3. The water content of the rubber particles after centrifugal drying is less than or equal to 3 percent.
4. The solid phase shearing grinder is a millstone type mechanochemical grinder, is a three-dimensional area formed by oppositely placing a movable disc and a static disc, and has the functions of room temperature ultrafine powder high polymer material, rapid micro-nano dispersion, solid phase capacity increase, solid phase mechanochemical reaction and the like; the material of the grinding surface tooth is high-quality alloy tool steel which is quenched, and the grinding surface tooth has excellent oxidation resistance, corrosion resistance and high temperature resistance.
5. The catalyst is one of alkali and solid super acid, wherein the alkali is potassium hydroxide, and the solid super acid is SbF5-SiO2 .TiO2、FSO3H-SiO2 .ZrO2, SbF5-TiO2 .ZrO2In one of the above, the particle size of the catalyst is 100-500 meshes, and the catalyst has the advantages of reduced thermal cracking initial temperature, shortened cracking time, more centralized monomer recovery, etc.
The invention has the beneficial effects that 1) the thermal cracking of the silicon rubber is effectively assisted by combining a physical crushing recovery method and a chemical catalytic cracking recovery method, so that the recovery rate and the single rate of the monomers are effectively improved, and the recovery benefit of the silicon rubber is improved; 2) the catalyst introduced by the invention is selected from one of alkali and solid super acid, so that the corrosion of equipment can be reduced, the dispersion efficiency of the catalyst is improved, the monomer recovery rate can be effectively improved, and the cracking process time can be shortened; 3) the monomer recovered by the method can be used as a raw material to produce various value-added materials, so that the aim of changing waste into valuable is fulfilled.
Drawings
FIG. 1 shows the weight loss ratio of the superfine rubber powder subjected to Soxhlet extraction.
FIG. 2 is a thermogravimetric plot of mechanochemical milling assisted thermal cracking of waste silicone rubber.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but it should not be construed that the scope of the present invention is limited to the examples.
Example 1
A mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method comprises the following preparation processes:
A. separating waste silicon rubber from a waste silicon rubber product (umbrella skirt on a waste composite insulator), crushing the waste silicon rubber into colloidal particles with the diameter of about 0.2 cm by using a wet crusher, centrifugally drying the colloidal particles, putting the dried colloidal particles into a solid phase shearing grinder for mechanochemical grinding for 1 time at the equipment pressure of 8 MPa and the rotating speed of 150 r/min to obtain superfine rubber powder, and then carrying out Thermogravimetry (TA), PY-GC/MS tests and Soxhlet extraction on the sample.
B. Compounding the superfine rubber powder with catalyst KOH, and then carrying out mechanochemical grinding for 1 time, wherein the using amount of KOH is 8wt% of the crushed rubber particles, so as to obtain the catalyst-containing superfine rubber powder; and subjected to Thermogravimetric (TA), PY-GC/MS tests.
C. And transferring the catalyst-containing superfine rubber powder into a pyrolysis furnace for thermal cracking, wherein the thermal cracking condition is that the thermal cracking is carried out for 3 hours at 180 ℃ in a nitrogen atmosphere.
The test result is shown in fig. 1 and 2, the weight loss rate eta of the superfine rubber powder subjected to Soxhlet extraction by the mechanochemical grinding is =2.83%, and is far higher than the eta of the colloidal particles which are not subjected to mechanochemical grinding by = 0.98%; the rubber powder Thermogravimetric (TG) initial degradation temperature (5% weight loss) is 271.21 ℃ without catalyst, 249.43 ℃ with catalyst, which are lower than those of the comparative example; the proportion of the collected crude DMC in the charged rubber powder was 54.89% without catalyst and 62.41% with catalyst, which were all higher than the comparative examples.
Example 2
A. Separating waste silicon rubber from a waste silicon rubber product (umbrella skirt on a waste composite insulator), crushing the waste silicon rubber into colloidal particles with the diameter of about 0.3 cm by using a wet crusher, centrifugally drying the colloidal particles, putting the dried colloidal particles into a solid phase shearing grinding machine for mechanochemical grinding for 3 times at the equipment pressure of 5 MPa and the rotating speed of 200 r/min to obtain superfine rubber powder, and then carrying out Thermogravimetry (TG), PY-GC/MS test and Soxhlet extraction on the sample.
B. Compounding the superfine rubber powder with catalyst KOH, and then carrying out mechanochemical grinding for 3 times, wherein the using amount of KOH is 8wt% of the crushed rubber particles, so as to obtain the catalyst-containing superfine rubber powder; and subjected to Thermogravimetric (TG), PY-GC/MS tests.
C. And transferring the catalyst-containing superfine rubber powder into a pyrolysis furnace for thermal cracking, wherein the thermal cracking condition is that the thermal cracking is carried out for 3 hours at 180 ℃ in a nitrogen atmosphere.
The test result is shown in fig. 1 and 2, the weight loss rate eta of the superfine rubber powder subjected to Soxhlet extraction by the mechanochemical grinding is =8.11%, and is far higher than the weight loss rate eta of colloidal particles which are not subjected to mechanochemical grinding = 0.98%; the rubber powder Thermogravimetric (TG) initial degradation temperature (5% weight loss) is 266.28 ℃ without catalyst and 236.79 ℃ with catalyst, which are lower than those of the comparative example; the proportion of the collected crude DMC in the charged rubber powder was 55.61% without catalyst and 63.47% with catalyst, which were all higher than the comparative examples.
Example 3
A. Separating waste silicon rubber from a waste silicon rubber product (umbrella skirt on a waste composite insulator), crushing the waste silicon rubber into colloidal particles with the diameter of about 0.4 cm by using a wet crusher, centrifugally drying the colloidal particles, putting the dried colloidal particles into a solid phase shearing grinder for mechanochemical grinding for 3 times at the equipment pressure of 5 MPa and the rotating speed of 100 r/min to obtain superfine rubber powder, and then carrying out Thermogravimetry (TA), PY-GC/MS tests and Soxhlet extraction on the sample.
B. Mixing superfine rubber powder with catalyst SbF5-SiO2.TiO2After compounding, performing mechanochemical grinding for 3 times to obtain SbF5-SiO2.TiO2The dosage of the superfine rubber powder is 8wt% of the crushed rubber particles to obtain the superfine rubber powder containing the catalyst; and subjected to Thermogravimetric (TA), PY-GC/MS tests.
C. And transferring the catalyst-containing superfine rubber powder into a pyrolysis furnace for thermal cracking, wherein the thermal cracking condition is that the thermal cracking is carried out for 3 hours at 180 ℃ in a nitrogen atmosphere.
The test results are shown in fig. 1 and 2, the initial degradation temperature (5% weight loss) of rubber powder by heat weight (TG) is 266.28 ℃ without catalyst, and the temperature with catalyst is 237.15 ℃ which are lower than those of the comparative example; the proportion of the collected crude DMC in the charged rubber powder was 55.61% without catalyst and 61.58% with catalyst, which were all higher than in the comparative example.
Comparative example
A. Separating waste silicon rubber from waste silicon rubber products (umbrella skirts on waste composite insulators), crushing the waste silicon rubber into colloidal particles with the diameter of 0.2 cm by using a wet crusher, centrifugally drying the colloidal particles, and then performing Thermogravimetry (TG), PY-GC/MS (propyl-GC-MS) tests and Soxhlet extraction on the samples.
B. Compounding the crushed colloidal particles with a catalyst KOH, wherein the using amount of the KOH is 8wt% of the crushed colloidal particles, and obtaining catalyst-containing colloidal particles; and subjected to Thermogravimetric (TG), PY-GC/MS tests.
C. And transferring the colloidal particles containing the catalyst into a pyrolysis furnace for thermal cracking, wherein the thermal cracking condition is that the thermal cracking is carried out for 3 hours at 180 ℃ in a nitrogen atmosphere.
D. And C, performing Soxhlet extraction on the silicon rubber particles prepared in the step A to obtain a small molecular weight loss rate eta =0.98% of only a crushed sample.
The test result is shown in fig. 1 and 2, the weight loss rate eta of the small molecule extracted by Soxhlet extraction of the non-mechanochemical ground colloidal particle is = 0.98%; the colloidal particle Thermogravimetric (TG) initial degradation temperature (5% weight loss) is 283.02 ℃ without catalyst and 266.27 ℃ with catalyst; the crude DMC obtained was collected in a proportion of the added colloidal particles of 45.59% without catalyst and 51.44% with catalyst.
Analysis and test conditions:
A. the thermogravimetric conditions were: the heating rate is 20 ℃/min, the temperature range is 30-900 ℃, and N2An atmosphere.
B. The extraction weight loss rate is as follows: soxhlet extraction is carried out on the prepared broken silicon rubber sample, and 1 g of the sample is weighed on an analytical balance and recorded as m1The number of the samples was 4, and the samples were wrapped with a copper mesh to prevent the samples from overflowing the solvent. Adding about 300 mL of normal hexane serving as an extraction solvent into a single-mouth flask, placing the single-mouth flask into a silicone oil pot at 90 DEG CIs carried out for 12 h at oil temperature. The 4 silicone rubber samples were taken out, dried in a vacuum drying oven at 60 ℃ under reduced pressure for 4 h and weighed again with the analytical balance. Repeating the reduced pressure drying process in the process until the mass difference is less than or equal to 2 mg after the reduced pressure drying for the two times, and recording the mass of the sample at the moment as m2. Calculating the extraction weight loss ratio (eta = (m)) according to the mass change of the sample before and after Soxhlet extraction1-m2)/m1X 100%) and the average of 4 samples was taken.
C. Cracking-gas chromatography:
and (3) cracking conditions: 550 ℃ for 12s, interface temperature: 300 ℃, GC injection port temperature: 320 ℃, split ratio: 30, column flow rate: 1ml/min, temperature rising program: 40 ℃ (constant temperature 1 min), 5 ℃/min to 80 ℃, 15 ℃/min to 300 ℃ (constant temperature 15 min), electron energy 70eV, ion source temperature 230 ℃, transmission line temperature 300 ℃, mass scanning range m/z 40-550, scanning mode: and (4) full scanning.
Claims (7)
1. A mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method is characterized by comprising the following steps:
A. separating waste silicon rubber from waste silicon rubber products, and crushing the separated waste silicon rubber into colloidal particles with the diameter of 0.1-5.0 cm by using a wet crusher;
B. centrifugally spin-drying the crushed colloidal particles, putting the dried colloidal particles into a solid-phase shearing grinder for mechanochemical grinding, wherein the equipment pressure is 1-10 MPa, the rotating speed is 80-200 r/min, and the grinding times are 1-5 times to obtain superfine colloidal powder;
C. compounding the superfine rubber powder with a catalyst, and then carrying out mechanochemical grinding, wherein the dosage of the catalyst is 5-8 wt%, so as to obtain the catalyst-containing superfine rubber powder;
D. and transferring the catalyst-containing superfine rubber powder into a pyrolysis furnace for thermal cracking under the condition of nitrogen atmosphere at 180 ℃ and 220 ℃ for 3 hours to obtain a recovered monomer.
2. The method as claimed in claim 1, wherein the mechanical grinding and chemical catalysis are combined to effectively assist thermal cracking of silicone rubber.
3. The mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method as claimed in claim 1, characterized in that the water content of the wet crusher is 50% -80%, the crushing blade is a claw knife type blade formed by combining a movable knife and a fixed knife, and the diameter of the screen is 0.1-5.0 cm.
4. The mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method as claimed in claim 1, wherein the water content of the rubber particles after centrifugal drying is less than or equal to 3%.
5. The mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method as claimed in claim 1, characterized in that the solid phase shearing grinding machine is a millstone type mechanical chemical grinding machine.
6. The method as claimed in claim 1, wherein the catalyst is a chemical catalyst selected from alkali and solid super acid.
7. The mechanical force chemical grinding assisted waste silicon rubber thermal cracking recovery method as claimed in claim 1, wherein the mechanical force chemical grinding after the compounding of the crushed colloidal particles and the catalyst comprises the following specific steps: the method for obtaining the catalyst-containing superfine rubber powder is that the catalyst and crushed silicon rubber particles are evenly compounded and then put into a grinder for grinding together.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB577829A (en) * | 1942-07-03 | 1946-06-03 | Frank Harriss Cotton | Process of reclaiming rubber |
| CN1597121A (en) * | 2004-07-19 | 2005-03-23 | 四川大学 | Method of preparation high surface activity rubber powder by waste tyre |
| WO2008131643A1 (en) * | 2007-04-25 | 2008-11-06 | Huihong Chen | Method and apparatus for combined recycling of waste polymer material or joint production with carbon black |
| CN102134331A (en) * | 2011-01-21 | 2011-07-27 | 合肥工业大学 | Recycling method of waste silicone rubber |
| CN103626796A (en) * | 2012-08-28 | 2014-03-12 | 杨晓林 | Recovery method of silicone rubber |
| CN103665870A (en) * | 2013-11-09 | 2014-03-26 | 国家电网公司 | Recovery and reutilization method of waste composite insulator silicon rubber material |
| CN111234309A (en) * | 2020-03-24 | 2020-06-05 | 广东省稀有金属研究所 | Method for recovering cyclosiloxane monomer by catalytic cracking of waste silicone rubber |
| CN112280164A (en) * | 2020-11-01 | 2021-01-29 | 福建师范大学 | Method for researching high-activity single-variety shoe material powder modification technology |
| WO2021168402A1 (en) * | 2020-02-20 | 2021-08-26 | Georgia Tech Research Corporation | Mechanocatalytic depolymerization of plastics |
| CN113547667A (en) * | 2021-06-04 | 2021-10-26 | 北京克林泰尔环保科技有限公司 | Waste rubber tire treatment method based on environmental protection |
| CN113563376A (en) * | 2021-07-08 | 2021-10-29 | 枣阳市一鸣化工有限公司 | Method for recovering waste silicon rubber |
-
2021
- 2021-11-12 CN CN202111342491.4A patent/CN114031636A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB577829A (en) * | 1942-07-03 | 1946-06-03 | Frank Harriss Cotton | Process of reclaiming rubber |
| CN1597121A (en) * | 2004-07-19 | 2005-03-23 | 四川大学 | Method of preparation high surface activity rubber powder by waste tyre |
| WO2008131643A1 (en) * | 2007-04-25 | 2008-11-06 | Huihong Chen | Method and apparatus for combined recycling of waste polymer material or joint production with carbon black |
| CN102134331A (en) * | 2011-01-21 | 2011-07-27 | 合肥工业大学 | Recycling method of waste silicone rubber |
| CN103626796A (en) * | 2012-08-28 | 2014-03-12 | 杨晓林 | Recovery method of silicone rubber |
| CN103665870A (en) * | 2013-11-09 | 2014-03-26 | 国家电网公司 | Recovery and reutilization method of waste composite insulator silicon rubber material |
| WO2021168402A1 (en) * | 2020-02-20 | 2021-08-26 | Georgia Tech Research Corporation | Mechanocatalytic depolymerization of plastics |
| CN111234309A (en) * | 2020-03-24 | 2020-06-05 | 广东省稀有金属研究所 | Method for recovering cyclosiloxane monomer by catalytic cracking of waste silicone rubber |
| CN112280164A (en) * | 2020-11-01 | 2021-01-29 | 福建师范大学 | Method for researching high-activity single-variety shoe material powder modification technology |
| CN113547667A (en) * | 2021-06-04 | 2021-10-26 | 北京克林泰尔环保科技有限公司 | Waste rubber tire treatment method based on environmental protection |
| CN113563376A (en) * | 2021-07-08 | 2021-10-29 | 枣阳市一鸣化工有限公司 | Method for recovering waste silicon rubber |
Non-Patent Citations (1)
| Title |
|---|
| 马超;赵林;卢灿辉;曾俊峰;: "固相力化学改性高聚物的方法研究" * |
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