CN101696285A - New method for activating and recycling tyre waste rubber powder - Google Patents
New method for activating and recycling tyre waste rubber powder Download PDFInfo
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- CN101696285A CN101696285A CN200910035658A CN200910035658A CN101696285A CN 101696285 A CN101696285 A CN 101696285A CN 200910035658 A CN200910035658 A CN 200910035658A CN 200910035658 A CN200910035658 A CN 200910035658A CN 101696285 A CN101696285 A CN 101696285A
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- 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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Abstract
The invention discloses a new method for activating and recycling tyre waste rubber powder, which belongs to the technical field of recycling waste rubbers. The process comprises the following steps: adding a fixed quantity of modifying agent into the waste rubber powder; extruding the mixture by using a screw extruder; heating, drying and cracking the waste rubber powder in the extruding process to ensure that a large number of cross bonds in the waste rubber powder are fractured; cooling the extruded waste rubber powder after microwave radiation, then activating the waste rubber powder, and mixing the activated waste rubber powder with universal rubbers such as natural rubber, cis-butadiene rubber, styrene butadiene rubber and the like to prepare a gross rubber; and vulcanizing the gross rubber. Tests show that a sample and a product containing the activated rubber powder have excellent performances, and the process is simple, convenient and efficient and has outstanding economic benefits and social benefits.
Description
Technical field
The present invention relates to waste old salvage material reutilization technology, be specifically related to the novel method that a kind of tyre waste rubber powder activation utilizes again.The activation that mainly is applicable to junked tire tread rubber rubber powder utilizes again.
Background technology
The quantity of waste old material is only second to plastic waste in spent high molecular material, wherein learies is more than 1,000,000,000 doughnut whole world year, and China is at 5000 ~ 6,000 ten thousand.The recycling of waste old is based on junked tire, and the utilization of waste rubber helps protecting environment, realizes the utilization again of resource, helps continuous development of society economy.At present progressively replaced the production of reclaimed rubber at shoddy aspect the recycling of developed country's waste old.
With rubber powder directly and other blend rubbers, the performance of products obtained therefrom all will sharply descend with the adding of rubber powder, this mainly be interface binding ability between the superpolymer of rubber powder and other forming process relatively poor due to.Therefore, interface modification is one of rubber powder key technologies for application.Activated rubber powder is for the performance that improves the rubber powder title complex chemically treated rubber powder to be carried out on its surface.The activation modification method of rubber powder is a lot of at present, roughly is divided into: grafting method; Interpenetrating polymer networks (IPN) method; Mechanochemical method; Lively atmosphere structural reform method; Polymer coating layer modification; The modification of nuclear-shell; Reclaimed rubber desulfurize modification and radiation method etc.
Radiation method has microwave method and gamma-rays method, wherein microwave method be a kind of non-chemically, a non-mechanical step desulfurization modification method, utilize microwave to cut off the sulfur-crosslinked key of rubber powder and do not cut off carbon-carbon bond, make the vulcanized rubber powder desulfurization and modified active.The Yangzhou University health likes that the red people of grade puts into the thermostatic drying chamber drying and dewatering with 80 order rubber powders, makes activated rubber powder after placing microwave device radiation certain hour then, can be used for the production of modifying asphalt; Qingdao University of Science and Technology's history the people such as is newly ground and is adopted the normal temperature method, WTPS small test chamber rubber powder system of processing with independent research, through the initial broken 10-30 order that separates, is crushed to steel-wire carcass, pulverize through pan-milling normal temperature again and make 80 order fineness rubber powders, this rubber powder is through ultrasonic wave and ozone surface treatment, and the surface of rubber powder particle has obtained certain activation; Human ultraviolet rays such as J.I.Kim are carried out surface modification to rubber powder, the while graft acrylamide, and the rubber powder after the modification is aided with maleic anhydride inoculated polypropylene with the HDPE blend time be compatilizer, obtains compatibilization effect preferably; People such as the Judd people adopt grafting interpenetrating polymer networks (IPN) method to study the mixture process shoddy that polyhutadiene type polyurethane prepolymer, vinylbenzene, divinylbenzene etc. are formed, rubber powder after the processing and natural rubber blend, its tensile strength reaches 19MPa, elongation at break reaches 640%, and performance only descends 5%.
After Yangzhou University's health likes that the red people of grade will activate the rubber powder particle surface metal spraying of front and back, adopting Kevex Super Rry energy spectrometer to test it can analyze the contained constituent content of rubber powder by spectrogram, find that rubber powder oxygen level after the microwave radiation activation obviously increases, the rubber powder contact angle increases, thereby improved the absorption property of rubber powder; In the reactivation process, microwave has destroyed S=S key, the C=S key in the rubber powder molecule in addition, and rubber powder partly is transformed into linear structure from original cross-linked network, and activity is significantly strengthened; But the distilled water contact angle testing experiment that rubber powder before and after the radiation carries out is found, after the microwave radiation activation, the contact angle of rubber powder increases, but along with radiation power increases, time lengthening, the contact angle of rubber powder diminishes again on the contrary, the proof microwave energy gathers can make more for a long time that established C-O key interrupts again, surface polarity descends, and illustrates that the microwave radiation activation treatment of rubber powder exists Best Times and power.
After Northwest Normal University (CN1597782) uses the softening agent swelling with 60-80 order waste rubber powder, with 360-900W microwave exposure 2-5min, make the structure division of waste rubber powder become more slick stratiform by particulate state, strengthened its physical and mechanical properties, be used for the matrix pitch modification and obtain good result; Hyundai (CN1733443) a kind of device that can carry out microwave treatment continuously to waste rubber powder from motor-car Co., Ltd. invention, utilize power to be not less than 0.5Kw but be not more than the microwave of 2Kw, under 150 ℃ of-250 ℃ of temperature, to particle diameter is the waste rubber powder radiation treatment 10-120S of 80 μ m-1000 μ m, obtains better activation effect; Qingdao University of Science and Technology (CN101157769) in a kind of preparation of chloroprene rubber and modification with combination treatment and ground fineness rubber powder, in microwave generator, use 800-1200W microwave exposure 5-15min, be used to prepare chloroprene rubber powder then, obtain certain effect.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art complex process, the novel method that provides a kind of tyre waste rubber powder activation to utilize again.This technological process and process facility are simple, and the rubber powder activation effect is outstanding, and the consistency of activated rubber powder and other superpolymer improves, and obviously improve with the shared back of superpolymer performance such as natural rubber.
The present invention realizes with following technical scheme: the novel method that a kind of tyre waste rubber powder activation utilizes again, it is characterized in that and to add the thick rubber powder of properties-correcting agent by after the cracking of screw extrusion press heat drying, microwave radiation and the air cooling, carry out with all-purpose gum kinds such as natural rubber, cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR) and use, adding Synergist S-421 95s such as vulcanizing agent, vulcanization accelerator and vulcanization leveller in the low temperature mill carries out mixing, make rubber unvulcanizate, realize that shoddy utilizes again;
Specifically may further comprise the steps:
(1) feeding device by screw extrusion press will add properties-correcting agent p tert butylphenol formaldehyde resin 2402
#Add screw extrusion press with the 10-30 order shoddy of pyrochemistry peptizer, mixture adds moisture in the heat extraction shoddy at the feeding section of forcing machine, and its Heating temperature is 100 ± 5 ℃, and the time is 3min; The extrusion shearing power of the screw compression section of forcing machine makes the sulphide bond of shoddy that a large amount of fractures take place, and the Heating temperature of compression section is 160 ± 5 ℃, by being heat-up time 5min; Wherein the properties-correcting agent p tert butylphenol formaldehyde resin 2402
#Adding can balanced compound system in the response capacity of each phase, the quality of each phase is reached unanimity substantially; Described pyrochemistry peptizer is pentachlorothiophenol or 2,2 '-dibenzoyl amido phenylbenzene disulphide, and the addition of chemical peptizer is 0.3～0.5% of a rubber powder quality;
(2) shoddy enters microwave radiation device while stirring after forcing machine is extruded, and carries out activation treatment with microwave radiation; The microwave radiation frequency of microwave device is 2450Hz, and power is 800W, and irradiation time is 2min;
(3) shoddy of crossing through the microwave radiation activation treatment is carried out air cooling, under 0-10 ℃, cool off 10min while stirring;
(4) will activate shoddy thin-pass about 8-12 time in the low temperature mill, roll spacing is 0.5～1.0mm, makes part chemical bond and cross-link bond produce power-chemistry fracture, makes quality more even;
(5) then in the low temperature mill with activated rubber powder and other blend rubbers, obtain blend glue stuff, described other rubber comprise all-purpose gum kinds such as natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR);
(6) in the low temperature mill, adding vulcanizing agent sulfur flour, vulcanization accelerator, vulcanization leveller ZnO and stearic acid in blend glue stuff successively carries out mixing, wherein promotor comprises accurate hypervelocity, ultra fast accelerator and super ultra fast accelerator, this three major types promotor comprises a lot of kinds, for example tetramethyl-thiuram disulfide (TT) obtains rubber unvulcanizate and obtains rubber unvulcanizate.
The consumption proportion by weight of each material is as follows in the above-mentioned technology:
25.0 parts of 30 order damaged tire tyre surface rubber powders
P tert butylphenol formaldehyde resin (2402
#) 3.0 parts
0.22 part of chemistry peptizer pentachlorothiophenol
25.0 parts of natural rubber NR
Sulfur flour S
81.25 part
0.30 part of accelerant N-cyclohexyl-2-benzothiazole sulfonamide
2.50 parts of zinc oxide ZnO
1.50 parts of stearic acid.
The invention has the beneficial effects as follows: the invention process step is simple, the production less investment, especially microwave radiation technology accurately, reliably, efficiently, the efficient height of rubber powder activation modification, effective, the rubber unvulcanizate that the waste old rubber powder makes, salient features excellence after tested, technology of the present invention can be brought outstanding economic benefit and social benefit, has wide market application prospect.
Description of drawings
Fig. 1 is a process flow diagram of the present invention;
Fig. 2 is concrete production scheme.
Embodiment
Further illustrate the solution of the present invention and effect below in conjunction with embodiment.
As depicted in figs. 1 and 2, be that 30 purpose waste and used rubber tyre tyre surface rubber powder 25.0kg add compatilizer resol 3.0kg, chemical peptizer 2 with granularity, extrude by screw extrusion press (XJ-250) behind the 2-dibenzoyl amido phenyl disulphide 0.2kg.Shoddy enters microwave radiation device while stirring after extruding, carry out activation treatment with microwave radiation, and the microwave radiation frequency of microwave device is 2450Hz, and power is 800W, and irradiation time is 2min.The shoddy of crossing through the microwave radiation activation treatment is carried out air cooling, under 0-10 ℃, cool off 10min while stirring.To activate the shoddy thin-pass in the low temperature mill (XK-160) about 10 times, roll spacing is 0.5～1.0mm.Then in the low temperature mill with activated rubber powder and natural rubber blend, obtain blend glue stuff.Again in the low temperature mill, adding vulcanizing agent sulfur flour, vulcanization accelerator, vulcanization leveller ZnO, stearic acid in blend glue stuff successively carries out mixing, wherein promotor comprises accurate hypervelocity, ultra fast accelerator and super ultra fast accelerator, this three major types promotor comprises a lot of kinds, for example tetramethyl-thiuram disulfide (TT) obtains rubber unvulcanizate.
With this rubber unvulcanizate by existing routine techniques sulfidizing after, the result who tests its film performance is: tensile strength 21MPa, elongation at break 640%, overall performance only descends 3% than pure natural rubber, this result shows that this waste old rubber powder microwave activation utilizes technology simply efficient again, and its activation levels and waste old rubber powder utilize effect obviously to be better than existing activation again and utilize technology again.
Claims (1)
1. a tyre waste rubber powder activates the novel method of utilizing again, it is characterized in that and to add the thick rubber powder of properties-correcting agent by after the cracking of screw extrusion press heat drying, microwave radiation and the air cooling, carry out with all-purpose gum kinds such as natural rubber, cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR) and use, adding Synergist S-421 95s such as vulcanizing agent, vulcanization accelerator and vulcanization leveller in the low temperature mill carries out mixing, make rubber unvulcanizate, realize that shoddy utilizes again;
Specifically may further comprise the steps:
(1) feeding device by screw extrusion press will add properties-correcting agent p tert butylphenol formaldehyde resin 2402
#Add screw extrusion press with the 10-30 order shoddy of pyrochemistry peptizer, mixture is at the feeding section of the forcing machine moisture in the heat extraction shoddy gradually, and its Heating temperature is 100 ± 5 ℃, and the time is 3min; The extrusion shearing power of the screw compression section of forcing machine makes the sulphide bond of shoddy that a large amount of fractures take place, and the Heating temperature of compression section is 160 ± 5 ℃, by being heat-up time 5min; Described pyrochemistry peptizer is pentachlorothiophenol or 2,2 '-dibenzoyl amido phenylbenzene disulphide, and addition is 0.3～0.5% of a rubber powder quality, the cross-link bond thermo-cracking efficient on shoddy surface is very high;
(2) shoddy enters microwave radiation device while stirring after forcing machine is extruded, and carries out activation treatment with microwave radiation; The microwave radiation frequency of microwave device is 2450Hz, and power is 800W, and irradiation time is 2min;
(3) shoddy of crossing through the microwave radiation activation treatment is carried out air cooling, under 0-10 ℃, cool off 10min while stirring;
(4) will activate shoddy thin-pass about 8-12 time in the low temperature mill, roll spacing is 0.5～1.0mm, makes part chemical bond and cross-link bond produce power-chemistry fracture, makes quality more even;
(5) then in the low temperature mill with activated rubber powder and other blend rubbers, obtain blend glue stuff, described other rubber comprise all-purpose gum kinds such as natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR);
(6) in the low temperature mill, in blend glue stuff, add vulcanizing agent sulfur flour, vulcanization accelerator, vulcanization leveller ZnO and stearic acid successively and carry out mixingly, wherein promotor comprises accurate hypervelocity, ultra fast accelerator and super ultra fast accelerator, obtains rubber unvulcanizate;
The consumption proportion by weight of each material is as follows in the above-mentioned technology:
25.0 parts of 30 order damaged tire tyre surface rubber powders
P tert butylphenol formaldehyde resin (2402
#) 3.0 parts
0.22 part of chemistry peptizer pentachlorothiophenol
25.0 parts of natural rubber NR
Sulfur flour S
81.25 part
0.30 part of accelerant N-cyclohexyl-2-benzothiazole sulfonamide
2.50 parts of zinc oxide ZnO
1.50 parts of stearic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100356585A CN101696285B (en) | 2009-09-30 | 2009-09-30 | New method for activating and recycling tyre waste rubber powder |
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| CN2009100356585A CN101696285B (en) | 2009-09-30 | 2009-09-30 | New method for activating and recycling tyre waste rubber powder |
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| CN101696285A true CN101696285A (en) | 2010-04-21 |
| CN101696285B CN101696285B (en) | 2011-11-23 |
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Cited By (23)
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|---|---|---|---|---|
| CN101879786A (en) * | 2010-06-25 | 2010-11-10 | 吴汉净 | Method of making environment-friendly sole by waste shoe |
| CN101974173A (en) * | 2010-10-18 | 2011-02-16 | 江汉大学 | Microwave activated waste rubber powder-containing flame retardant rubber plate and preparation method thereof |
| CN102010531A (en) * | 2010-11-17 | 2011-04-13 | 安徽安大中鼎橡胶技术开发有限公司 | Modified-surface activated waste vulcanizate powder |
| CN104844818A (en) * | 2015-05-14 | 2015-08-19 | 安徽红太阳新材料有限公司 | Novel energy-saving and environment-friendly reclaimed rubber production process |
| CN105037865A (en) * | 2015-08-20 | 2015-11-11 | 华南理工大学 | Modified scrap rubber powder as well as preparation method and application thereof |
| CN105254944A (en) * | 2015-10-20 | 2016-01-20 | 苏州蔻美新材料有限公司 | Material for production of hot-water bags and preparation method of material |
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| CN105330922A (en) * | 2015-10-28 | 2016-02-17 | 贵州安泰再生资源科技有限公司 | Method of recycling rubber powder of junked tires through activation |
| CN105330892A (en) * | 2015-10-28 | 2016-02-17 | 贵州安泰再生资源科技有限公司 | Method for preparing rubber powder by desulfurizing waste tires at low temperature through ammonia method |
| CN105330888A (en) * | 2015-10-28 | 2016-02-17 | 贵州安泰再生资源科技有限公司 | Method of stirring rubber powder of junked tires for desulfuration |
| CN105399984A (en) * | 2015-10-28 | 2016-03-16 | 贵州安泰再生资源科技有限公司 | Desulfurizing agent for comprehensive utilization of waste tires as well as preparation method and application method thereof |
| CN105754173A (en) * | 2016-03-13 | 2016-07-13 | 北京化工大学 | Low-cost and efficient method using devulcanized rubber powder to directly prepare rubber compound |
| CN109679179A (en) * | 2018-12-29 | 2019-04-26 | 甘肃兰煤机械制造有限公司 | A kind of reuse method of waste and old mining machinery tire |
| WO2019145743A1 (en) * | 2018-01-26 | 2019-08-01 | Reca Blend Kft. | Recycling of vulcanized rubber products |
| CN110128723A (en) * | 2019-05-29 | 2019-08-16 | 浙江通超工贸有限公司 | A kind of high-mechanic solid tyre rubber and preparation method thereof |
| CN110564029A (en) * | 2019-09-26 | 2019-12-13 | 徐州工业职业技术学院 | Preparation method of high-performance low-cost rubber powder-based composite elastomer |
| CN111234310A (en) * | 2020-03-30 | 2020-06-05 | 泸州正发新材料有限公司 | Preparation method of fine rubber powder of activated waste rubber |
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| CN111363215A (en) * | 2020-01-13 | 2020-07-03 | 沈阳化工大学 | Preparation method of BR/SBR/tread reclaimed rubber/rubber powder combined truck tire pad belt |
| CN111363216A (en) * | 2020-01-15 | 2020-07-03 | 沈阳化工大学 | Method for preparing truck tire pad belt by using reclaimed rubber and rubber powder together |
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| CN1100083C (en) * | 2000-04-14 | 2003-01-29 | 广州市再生资源利用研究所 | Process for regenerating waste or used vulcanized rubber |
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- 2009-09-30 CN CN2009100356585A patent/CN101696285B/en not_active Expired - Fee Related
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|---|---|---|---|---|
| CN101879786A (en) * | 2010-06-25 | 2010-11-10 | 吴汉净 | Method of making environment-friendly sole by waste shoe |
| CN101974173A (en) * | 2010-10-18 | 2011-02-16 | 江汉大学 | Microwave activated waste rubber powder-containing flame retardant rubber plate and preparation method thereof |
| CN101974173B (en) * | 2010-10-18 | 2013-07-17 | 江汉大学 | Microwave activated waste rubber powder-containing flame retardant rubber plate and preparation method thereof |
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| CN109679179A (en) * | 2018-12-29 | 2019-04-26 | 甘肃兰煤机械制造有限公司 | A kind of reuse method of waste and old mining machinery tire |
| CN110128723A (en) * | 2019-05-29 | 2019-08-16 | 浙江通超工贸有限公司 | A kind of high-mechanic solid tyre rubber and preparation method thereof |
| CN110564029A (en) * | 2019-09-26 | 2019-12-13 | 徐州工业职业技术学院 | Preparation method of high-performance low-cost rubber powder-based composite elastomer |
| CN111333936A (en) * | 2020-01-13 | 2020-06-26 | 沈阳化工大学 | Preparation method of NR/BR/tread reclaimed rubber/rubber powder combined truck tire pad belt |
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| CN114919109A (en) * | 2022-05-20 | 2022-08-19 | 广西科学院 | Method for vulcanizing rubber by utilizing microwaves |
| CN114919109B (en) * | 2022-05-20 | 2024-02-20 | 广西科学院 | Method for vulcanizing rubber by utilizing microwaves |
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| CN101696285B (en) | 2011-11-23 |
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