CN106674589A - Method for desulfurating waste tyre powder by utilizing waste edible oil and preparation method of modified asphalt - Google Patents
Method for desulfurating waste tyre powder by utilizing waste edible oil and preparation method of modified asphalt Download PDFInfo
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- CN106674589A CN106674589A CN201610964935.0A CN201610964935A CN106674589A CN 106674589 A CN106674589 A CN 106674589A CN 201610964935 A CN201610964935 A CN 201610964935A CN 106674589 A CN106674589 A CN 106674589A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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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
- C08J2317/00—Characterised by the use of reclaimed rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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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- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for desulfurating waste tyre powder by utilizing waste edible oil. The method comprises the following steps: (1) uniformly mixing the waste edible oil with the waste tyre powder, wherein the mass ratio of the waste edible oil to the waste tyre powder is (3-8):(2-7); and (2) when the mixture of the edible oil and the waste tyre powder in the step (1) is heated to 220 to 280 DEG C, carrying out heat-preservation stirring for 30 to 240 min so as to prepare desulfurated waste tyre powder. The invention also discloses a preparation method of a modified asphalt. The desulfurated waste tyre powder obtained in the method and a substrate asphalt are taken as raw materials. The preparation method comprises the following steps: (1) heating the substrate asphalt to be melted in the processing temperature range of 120 to 160 DEG C, slowly adding the desulfurated waste tyre powder, and uniformly stirring; and (2) heating the asphalt mixture obtained in the step (1) to 170 to 180 DEG C, and stirring for 15 to 60 min, so as to obtain the modified asphalt. The method is high in desulfuration degree and simple and environment-friendly in technology.
Description
Technical field
The present invention relates to the technology of preparing of the pre- desulfurization technology of waste rubber tyre powder and modified pitch, and in particular to waste edible oil pair
The method of waste rubber tyre powder desulfurization and a kind of preparation method of modified pitch.
Background technology
With the fast development of automobile industry, pollution problem of the junked tire to environment is increasingly severe, it is contemplated that the year two thousand twenty
Junked tire yield will be more than 20,000,000 tons.In order to rationally process junked tire, the regeneration of resource, country's outflow are realized
It is about to junked tire and makes rubber powder for asphalt modification, and asphalt by modification of waste tyre rubber powder concrete is because of its excellent pavement performance acquisition
Consistent affirmative both domestic and external.But, when waste rubber tyre powder is used as asphalt modifier, because waste rubber tyre powder and matrix pitch are being changed
Learn the aspects such as structure, density, viscosity, molecular weight and there is very big difference, it is thermodynamically extremely incompatible, cause waste rubber tyre powder to be modified
There is isolation in pitch, become the key issue of restriction asphalt by modification of waste tyre rubber powder popularization and application.
To solve the thermal storage stability of asphalt by modification of waste tyre rubber powder, generally pre- desulfurization is carried out to rubber powder, by by rubber powder
Desulfurization cracks to improve its compatibility with pitch.But at present all there is rubber powder desulfurization, cracking degree not in the pre- desulfurization technology of rubber powder
Foot, it is difficult to the problems such as stably storing in pitch.And the discharge of a large amount of hydrogen sulfide gas can also pollute in the pre- sweetening process of rubber powder
Environment.Such as using coal tar as auxiliary agent, toxicity is big, and the pollution to environment can not be ignored；Microwave, twin-screw extrusion desulfurization
Also there is a problem of relatively costly.
Can be very good to improve rubber powder based on the Terminal Blend rubber powder modified asphalt technologies of high temperature desulfurizing, cracking and change
Property pitch heat-storage stable problem, be current most successful rubber powder modified asphalt technology.But this technology is applied at home
There is shortcoming：The flash-point of road asphalt is typically relatively low.At present a large amount of asphalt production enterprises are produced using the auspicious oil of agate of Venezuela
Pitch, makes this problem more project, and its flash-point can only reluctantly reach technical requirements.If at the low pitch long-time of flash-point
Under ultra-high temperature condition, on the one hand easily there is burning with blast；On the other hand a large amount of light components volatilizations can make ageing of asphalt, and
The light components of volatilization are difficult to reclaim, and can also increase cost and pollution environment.Even if using the higher Imported Asphalt of flash-point, also according to
So there is ageing of asphalt, volatilization and safety problem.Although the colloid mill that the enterprises such as domestic precious profit pitch adopt grinding technique repeatedly
Reaction temperature can be reduced, but because temperature is higher, still suffers from firing phenomenon, and the technique working (machining) efficiency is relatively low, it is relatively costly.
Research to Terminal Blend rubber powder modified asphalt mechanism in the world shows, rubber powder is entered in liquid environment
Row high temperature desulfurizing, cracking, it is easier to control reaction process, improve waste rubber tyre powder desulfurization cracking degree.And a kind of flash-point height is found,
It is not volatile in high temperature environments, and the pitch alternative materials for having excellent compatibility with pitch crack solvent as rubber powder desulfurization,
Become the key for solving prior art problem.
With the continuous improvement of people's living standard, the various edible oil consumption figures of China are continuously increased, according to related data
Statistics, up to 26,000,000 tons, about 10% is using the only aggregate consumption of 1 year China's edible oil in 2015 in consumption edible oil
After go out of use, generate 2,600,000 tons of waste edible oil.It can be seen that, pollution problem of the waste edible oil to environment is increasingly serious.In addition,
A large amount of secondary dining tables that flow to of waste edible oil can also have a strong impact on the healthy of people.With increasingly in short supply, the tool of petroleum resources
There are high temperature resistant and pitch that there is the waste edible oil of excellent compatibility to become the preferred material of replacing asphalt cementitious matter.It can be seen that, adopt
Waste edible oil carries out pre- desulfurization to rubber powder, not only can solve the pre- desulfurization technology of rubber powder, the drip of Terminal Blend rubber powder modifieds
The problem that blue or green technology is present, and the regeneration of waste edible oil can be realized, the process for waste edible oil provides rational solution
Certainly scheme.
The content of the invention
The purpose of the present invention is to overcome defect of the prior art, there is provided a kind of desulfurization degree height, process is simple and environmental protection
The method with waste edible oil to waste rubber tyre powder desulfurization.
The present invention solves the technical scheme that its technical problem is adopted：A kind of side with waste edible oil to waste rubber tyre powder desulfurization
Method, comprises the following steps：
(1) waste edible oil is well mixed with waste rubber tyre powder, wherein waste edible oil and the mass ratio of waste rubber tyre powder are 3~8：
2~7；
(2) when the mixture of the edible oil of step (1) and waste rubber tyre powder being heated into 220 DEG C~280 DEG C, insulated and stirred 30
~240min, you can prepare the waste rubber tyre powder of desulfurization.
Preferably, waste edible oil described in step (1) is 5~7 with the mass ratio of waste rubber tyre powder：3~5.
The acid number of the waste edible oil is 3~10%, and flash-point is 280~310 DEG C.
Waste rubber tyre powder junked tire Jing powder by made by natural rubber, butadiene-styrene rubber, butadiene rubber or isoprene rubber
Broken to be obtained, the granularity of the waste rubber tyre powder is between 20~200 mesh.
It is a further object of the present invention to provide a kind of preparation method of modified pitch, using matrix pitch and said method system
The waste rubber tyre powder of the standby desulfurization for obtaining is raw material, is comprised the steps：
(1) matrix pitch is heated into molten condition, processing temperature scope is 120~160 DEG C, being slowly added to will with right
The stirring of the waste rubber tyre powder after 1 method desulfurization is asked to be well mixed it；
(2) asphalt mixture that step (1) is obtained is heated into 170~180 DEG C, stirs 15~60min, that is, be modified
Pitch.
The invention has the beneficial effects as follows：
(1) present invention adopts waste edible oil as the pre- desulfurization solvent of waste rubber tyre powder, with high temperature resistant and bitumen compatibility
The advantages of good；Using the pre- desulfurization powder of waste edible oil, rubber powder desulfurization cracking degree is high, is remarkably improved rubber powder compatible with pitch
Property, improve the thermal storage stability of rubber powder modified asphalt.
(2) waste rubber tyre powder that obtains of the pre- sulfur method of waste edible oil in the present invention, it is to avoid rubber powder is directly in matrix pitch
During middle cracking, burning easily occurs pitch long-time under ultra-high temperature condition and blast, ageing of asphalt, cost increase and environment is dirty
The problems such as dye, solve the problems, such as Terminal Blend rubber powder modified asphalt technologies.
(3) process is simple, it is safe, be conducive to the raising of batch production efficiency.
(4) waste edible oil is all waste and old salvage material with waste rubber tyre powder, is the regeneration of waste edible oil and waste tire
Rational solution is provided, is reduced its pollution and waste edible oil to environment and is returned harm of the dining table to human body.
(5) modified pitch prepared using the waste rubber tyre powder of the pre- desulfurization of waste edible oil, with good thermal storage stability
And cryogenic property.
Specific embodiment
With reference to embodiment, the invention will be further described, but not thereby limiting the invention.
According to patent methods described of the present invention and step, the waste rubber tyre powder of 8 desulfurization is prepared for respectively, embodiment 1~8 has
Preparation is operated in accordance with the following steps：
(1) waste edible oil (can be placed 1~48h, also can be directly carried out with being well mixed under waste rubber tyre powder room temperature after mixing
Next step is operated), the source of waste edible oil is the oil recovery after the edible oil refinement after discarding, such as waste oil etc., Ke Yi
On the market directly buying is arrived；The acid number of waste edible oil is 3%~10%, and flash-point is 280 DEG C~310 DEG C.The granularity of waste rubber tyre powder
Between 20~200 mesh, waste rubber tyre powder junked tire by made by natural rubber, butadiene-styrene rubber, butadiene rubber or isoprene rubber
It is size-reduced to be obtained.
(2) when mixed waste edible oil and waste rubber tyre powder mixture being heated into 220 DEG C~280 DEG C, insulated and stirred 30
~240 minutes, prepare the waste rubber tyre powder of desulfurization.
Ju Ti Pei Fang, operating parameter and evaluation result be shown in Table 1 in embodiment 1~8.1 is evaluated by same evaluation test method
Individual comparative example, the comparative example 1 being shown in Table in 1.
The desulfurized effect contrast table of the different formulations waste edible oil desulfurization waste rubber tyre powder of table 1
Method of testing：1. rubber powder solubility, %：Wherein S represents rubber powder solubility；m1Represent sample
Quality；m2Represent the quality of residue；R represents rubber powder ratio in the sample.
2. glue oil mixture viscosity, mPas：Chinese T 0625-2011
3. rubber powder remains rubber hydrocarbon, %：Chinese GB/T 14837-93.
4. glue oil mixture weight average molecular weight：With polystyrene standards；Using 0.22 μm of membrane filtration；Chromatographic column is adopted
The root chromatogram columns of TSK gel superHZM-M 6.0*150mm and TSK gel superHZ30006.0*150mm two are connected, column temperature
40℃；Mobile phase adopts tetrahydrofuran, flow velocity 0.6ml/min；Differential refraction detector temperature sets 40 DEG C.
As can be seen from Table 1, contrast with undesulfured rubber powder, Jing after the cracking of waste edible oil high temperature desulfurizing, waste rubber tyre powder is handed over
Networking network macromolecular content is reduced, and the small molecule content dissolved in organic solvent increases, and the crosslinking degree of rubber powder is reduced, rubber powder
Granular size diminishes.
After being prepared as described above the waste rubber tyre powder of desulfurization, the waste rubber tyre powder that above-described embodiment 1~8 is obtained is adopted
Stirring technique processing prepares modified pitch, and the concrete grammar for preparing modified pitch is operated as follows：
(1) matrix pitch is heated into molten condition, processing temperature scope is 120~160 DEG C, is slowly added to above-mentioned Jing and gives up
Waste rubber tyre powder after the pre- desulfurization of edible oil, stirring is well mixed it.
(2) asphalt mixture that step (1) is obtained is heated into 170~180 DEG C, stirs 15~60min so as to prepare
The modified pitch prepared with pre- desulfurization waste rubber tyre powder.
Experimental group 1~8 has been respectively adopted the desulfurization waste rubber tyre powder that previous embodiment 1~8 is prepared, Ju Ti Pei Fang, ginseng
Number and evaluation result are shown in Table 2, prepare 1 comparative example with step in the same way, and Ju Ti Pei Fang and evaluation result are shown in Table in 2
Contrast groups 1.
Performance of modified bitumen contrast table prepared by the desulfurization powder of the different formulations of table 2
Method of testing：1. modified pitch softening point, DEG C：ASTM D36, Chinese T 0606-2000
2. modified pitch BBR index Ss, Mpa, m：AASHTO：TP1-98
3. modified pitch isolation experiment, DEG C：Chinese T 0661-2011
4. modified pitch DSR indexs G*/sin δ, Pa：AASHTO TP5-93
As can be seen from Table 2, compared with undesulfured waste rubber tyre powder (contrast groups 1), using the useless of the pre- desulfurization of waste edible oil
The isolation experiment softening point difference △ t of tire rubber powder modified asphalt (experimental group 1~8) is respectively less than and (the contrast of undesulfured waste rubber tyre powder
Example 1) isolation experiment softening point difference △ t, cryogenic property also makes moderate progress.It can be seen that, using the pre- desulfurization waste rubber tyre powder of waste edible oil
The modified pitch of preparation, with good thermal storage stability and cryogenic property.
Claims (5)
1. a kind of method with waste edible oil to waste rubber tyre powder desulfurization, it is characterised in that：Comprise the following steps：
(1) waste edible oil is well mixed with waste rubber tyre powder, wherein waste edible oil and the mass ratio of waste rubber tyre powder are 3~8：2~
7；
(2) when the mixture of the edible oil of step (1) and waste rubber tyre powder being heated into 220 DEG C~280 DEG C, insulated and stirred 30~
240min, you can prepare the waste rubber tyre powder of desulfurization.
2. the method with waste edible oil to waste rubber tyre powder desulfurization according to claim 1, it is characterised in that：In step (1)
The waste edible oil is 5~7 with the mass ratio of waste rubber tyre powder：3~5.
3. the method with waste edible oil to waste rubber tyre powder desulfurization according to claim 1 and 2, it is characterised in that：It is described useless
The acid number of edible oil is 3~10%, and flash-point is 280~310 DEG C.
4. the method with waste edible oil to waste rubber tyre powder desulfurization according to claim 1 and 2, it is characterised in that：It is described useless
Tire rubber powder junked tire by made by natural rubber, butadiene-styrene rubber, butadiene rubber or isoprene rubber is size-reduced to be obtained, the damaged tire
The granularity of rubber powder is between 20~200 mesh.
5. a kind of preparation method of modified pitch, it is characterised in that：It is prepared into using matrix pitch and by the method for claim 1
The waste rubber tyre powder of the desulfurization arrived is raw material, is comprised the steps：
(1) matrix pitch is heated into molten condition, processing temperature scope is 120~160 DEG C, is slowly added to claim 1
Method desulfurization after waste rubber tyre powder, stirring be well mixed it；
(2) asphalt mixture that step (1) is obtained is heated into 170~180 DEG C, stirs 15~60min, that is, obtain modified drip
It is blue or green.
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892821A (en) * | 2017-12-19 | 2018-04-10 | 重庆路面科技有限公司 | Low viscosity suppression cigarette modified rubber asphalt composition and preparation method thereof |
| CN109705587A (en) * | 2018-08-24 | 2019-05-03 | 济南圣泉集团股份有限公司 | Rubber powder modified agent, multiplicity reactivation rubber powder and preparation method thereof, composite modified asphalt and preparation method thereof |
| CN110079105A (en) * | 2019-04-26 | 2019-08-02 | 同济大学 | A kind of sepiolite supported dissolubility rubber powder modified asphalt and preparation method thereof |
| CN110079106A (en) * | 2019-04-26 | 2019-08-02 | 同济大学 | A kind of dissolubility rubber powder modified asphalt of high-storage stability |
| WO2019214096A1 (en) * | 2018-05-11 | 2019-11-14 | 江苏宝利国际投资股份有限公司 | High-rubber asphalt masterbatch and low-temperature environmentally-friendly manufacturing process thereof |
| WO2019214097A1 (en) * | 2018-05-11 | 2019-11-14 | 江苏宝利国际投资股份有限公司 | Low-temperature environmental-friendly high-rubber asphalt having high performance and production process therefor |
| CN115160806A (en) * | 2022-07-18 | 2022-10-11 | 甘肃公航旅低碳科技有限公司 | Preparation method and application of low-carbon asphalt based on recycled resources |
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| CN102838874A (en) * | 2012-09-17 | 2012-12-26 | 山东建筑大学 | Asphalt modifier, modified asphalt and asphalt mixture |
| CN103819825A (en) * | 2014-01-27 | 2014-05-28 | 江苏爱特恩高分子材料有限公司 | Preparation method of environment-friendly reclaimed butyl rubber |
| CN104559262A (en) * | 2015-01-14 | 2015-04-29 | 长安大学 | Energy-saving environment-friendly asphalt and preparation method thereof |
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| CN102838874A (en) * | 2012-09-17 | 2012-12-26 | 山东建筑大学 | Asphalt modifier, modified asphalt and asphalt mixture |
| CN103819825A (en) * | 2014-01-27 | 2014-05-28 | 江苏爱特恩高分子材料有限公司 | Preparation method of environment-friendly reclaimed butyl rubber |
| CN104559262A (en) * | 2015-01-14 | 2015-04-29 | 长安大学 | Energy-saving environment-friendly asphalt and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892821A (en) * | 2017-12-19 | 2018-04-10 | 重庆路面科技有限公司 | Low viscosity suppression cigarette modified rubber asphalt composition and preparation method thereof |
| CN107892821B (en) * | 2017-12-19 | 2020-07-17 | 重庆路面科技有限公司 | Low-viscosity smoke-suppressing modified rubber asphalt composition and preparation method thereof |
| WO2019214096A1 (en) * | 2018-05-11 | 2019-11-14 | 江苏宝利国际投资股份有限公司 | High-rubber asphalt masterbatch and low-temperature environmentally-friendly manufacturing process thereof |
| WO2019214097A1 (en) * | 2018-05-11 | 2019-11-14 | 江苏宝利国际投资股份有限公司 | Low-temperature environmental-friendly high-rubber asphalt having high performance and production process therefor |
| CN109705587A (en) * | 2018-08-24 | 2019-05-03 | 济南圣泉集团股份有限公司 | Rubber powder modified agent, multiplicity reactivation rubber powder and preparation method thereof, composite modified asphalt and preparation method thereof |
| CN110079105A (en) * | 2019-04-26 | 2019-08-02 | 同济大学 | A kind of sepiolite supported dissolubility rubber powder modified asphalt and preparation method thereof |
| CN110079106A (en) * | 2019-04-26 | 2019-08-02 | 同济大学 | A kind of dissolubility rubber powder modified asphalt of high-storage stability |
| CN115160806A (en) * | 2022-07-18 | 2022-10-11 | 甘肃公航旅低碳科技有限公司 | Preparation method and application of low-carbon asphalt based on recycled resources |
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