CN105542817B - A kind of thermosol depolymerization junked tire is the method for rubber powder - Google Patents
A kind of thermosol depolymerization junked tire is the method for rubber powder Download PDFInfo
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- CN105542817B CN105542817B CN201510908326.9A CN201510908326A CN105542817B CN 105542817 B CN105542817 B CN 105542817B CN 201510908326 A CN201510908326 A CN 201510908326A CN 105542817 B CN105542817 B CN 105542817B
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- Prior art keywords
- ionic liquid
- junked tire
- rubber powder
- tetrahydrofuran
- naphthane
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
-
- 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
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a kind of method that thermosol depolymerization junked tire is rubber powder, belong to junked tire technical field of comprehensive utilization.The present invention is added junked tire and ionic liquid and hydrogen supply dissolvent in reactor, in a mild condition progress thermosol depolymerization by the ionic liquid and hydrogen supply dissolvent of the efficient disaggregation of waste and old tire construction of selection energy；Then the reaction product of gained is washed out with tetrahydrofuran, the mixed liquor and residue of tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane can be obtained by filtering, mixed liquor can obtain mixture by rotating solvent-recoverable；It is last toward water sedimentation is added in mixture and filtering can obtain the mixed solution of rubber powder and ionic liquid and naphthane, the mixed solution of ionic liquid and naphthane is reusable.This method technique is simple, process is clean；Can not only thermosol depolymerization be carried out to junked tire, while the thermosol depolymerization that can be catalyzed tire is rubber powder and carbon black, reaches the high value added utilization to junked tire.
Description
Technical field
The invention belongs to junked tire technical field of comprehensive utilization, relate in particular to it is a kind of using thermosol Depolymerization Technique come
Disaggregation of waste and old tire is the method and technique of rubber powder.
Background technology
The current tire learies in China rank the first in the world, and annual caused junked tire reclaims more than 10,000,000 tons
Utilization rate is only 60%, less than the utilization rate of developed country 90% or so.It is 300,000,000 a plurality of, weight that 2013, which produce junked tire,
Up to 15,000,000 tons, about 5,300,000 tons of natural rubber resource, natural rubber yield of 6.5 years equivalent to China are converted into.Junked tire is
Need to take the waste of a large amount of environment spaces, and be difficult to compress, collect and eliminate, and do not have biological degradability.Its into
Dividing also includes some dangerous elements, and such as lead, chromium, cadmium and other heavy metals, human health and environment are threatened.
Junked tire, which recycles, substantially 3 kinds of whole utilization, regeneration and heat utilization modes.Whole utilization is to useless wheel
Tire carries out overall utilization, and such as progress old tire renovation processing is allowed to recover original purposes or junked tire builds up green noise reduction
Wall；Regeneration is that damaged tire is made into reclaimed rubber or rubber powder, to produce vulcanized rubber powder or reclaimed rubber, junked tire production
Volatile organic contaminant can be produced during reclaimed rubber.Phase late 1980s, American-European major industrial country have stopped
The production of universal reclaimed rubber, the stage is directly utilized into vulcanized rubber powder.Heat utilization is divided to pyrolytic and directly two classes of burning.
Heat energy utilization is exactly to replace fuel to use with damaged tire, and damaged tire burning recovers energy, and there may be bioxin, furans, more cyclophanes
The pollutant such as hydrocarbon and heavy metal.
Waste tyre pyrolytic is to open chemical chain using external heat, organic matter is resolved into fuel gas, rich in aromatic hydrocarbon
The valuable chemical products such as oil and carbon black.Junked tire can be produced by high temperature pyrolysis about 45% fuel oil, 35%
Carbon black, 10% steel wire, it there is also about 10% and do not condense combustible gas.Murena(Journal of Hazardous
Materials, 1996,50 (1):Naphthane 79-98) is used to carry out hydropyrolysis as hydrogen supply agent to junked tire and ground
Study carefully, it is found that the quality of solid residue falls below 34% by 43%, pyrolysis oil yield has brought up to 50%-60% by 44%.But
Pyrolytic technique is complicated, cost is high, easily causes secondary pollution, and it is again unstable to reclaim material quality defect.
The content of the invention
For overcome the deficiencies in the prior art, the invention aims to provide one kind to give up come depolymerization using thermosol Depolymerization Technique
Old tire is the method for rubber powder.
To achieve the above object, the technical solution adopted by the present invention is：
(1) selection can efficiently destroy the ionic liquid and hydrogen supply dissolvent of junked tire structure, by junked tire, hydrogen supply dissolvent
Reactor is added to ionic liquid, the wherein mass ratio of ionic liquid, hydrogen supply dissolvent and junked tire is 1~5:1~20:
1；
(2) the mixture heating that is formed ionic liquid, hydrogen supply dissolvent and junked tire, temperature control room temperature~
400 DEG C, react 0.5~4 hour, reaction naturally cools to room temperature after terminating；
(3) reaction product of gained is washed out with tetrahydrofuran, tetrahydrofuran DDGS, tetrahydrochysene furan can be obtained by filtering
Mutter, the mixed liquor and residue of ionic liquid and naphthane, mixed liquor can obtain mixture by rotating recycling design；
(4) it is last toward add water sedimentation in mixture and filtering can obtain rubber powder and ionic liquid and naphthane mixing it is molten
The mixed solution of liquid, ionic liquid and naphthane is reusable.
The ionic liquid is the 1- butyl -3- methylimidazole trifluoromethanesulfonic acids for having to junked tire preferable damage capability
Salt.The hydrogen supply dissolvent is naphthane.
Optimize as one kind, in the step (1)：The mass ratio of ionic liquid, hydrogen supply dissolvent and junked tire is 5:
20:1；In the step (2)：The mixture that ionic liquid, hydrogen supply dissolvent and junked tire are formed is heated to reacting at 250 DEG C
2h。
Compared with prior art, the present invention has following technique effect：
1st, using thermal-dissolving way at low temperature Depolymerization Technique be it is a kind of can be by the phase between junked tire and depolymerization solvent in low temperature
The structure that interaction in interaction and tire between each material comes between each component of disaggregation of waste and old tire.Profit of the invention
Efficient heat of solution is carried out to junked tire to gather, can not only carry out heat of solution to junked tire with hydrogen supply dissolvent and ionic liquid
It is poly-, while the thermosol depolymerization that can be catalyzed tire is rubber powder and carbon black, reaches the high value added utilization to junked tire.
2nd, thermosol de-polymerization temperature of the present invention is low (room temperature~400 DEG C), process stabilizing, and easily controllable and technological operation is simple.
3rd, the economy that can effectively improve process can be recycled in ionic liquid and hydrogen supply dissolvent of the present invention.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment, but the present invention is not limited to following embodiments.
Embodiment 1
Weigh 5g 1- butyl -3- methylimidazoles fluoroform sulphonate, 2ml naphthanes and 1g junked tire mix it is rearmounted
Vibrated in tubular type in kettle, react 4h at 50 DEG C.Reaction naturally cools to room temperature after terminating；Then the reaction product of gained is used
Tetrahydrofuran is washed out, and the mixed liquor of tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane and residual can be obtained by filtering
Slag, mixed liquor can obtain mixture by rotating solvent-recoverable；It is last to obtain glue toward addition water sedimentation in mixture and filtering
The mixed solution of the mixed solution of powder and ionic liquid and naphthane, ionic liquid and naphthane is reusable.Rubber powder is claimed
Weigh and calculate the yield of rubber powder.The yield of gained rubber powder is 30.1%.
Embodiment 2
Weigh 1g 1- butyl -3- methylimidazoles fluoroform sulphonate, 10ml naphthanes and 1g junked tire mix after
It is placed in tubular type vibration kettle, reacts 2h at 150 DEG C.Reaction naturally cools to room temperature after terminating；Then the reaction of gained is produced
Thing is washed out with tetrahydrofuran, and the mixed liquor of tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane can be obtained by filtering
And residue, mixed liquor can obtain mixture by rotating solvent-recoverable；Finally can toward addition water sedimentation in mixture and filtering
Rubber powder and ionic liquid and naphthane mixed solution, the mixed solution of ionic liquid and naphthane is reusable.By glue
Powder is weighed and calculates the yield of rubber powder.The yield of gained rubber powder is 55.9%.
Embodiment 3
Weigh 5g 1- butyl -3- methylimidazoles fluoroform sulphonate, 2ml naphthanes and 1g junked tire mix it is rearmounted
Vibrated in tubular type in kettle, react 3h at 250 DEG C.Reaction naturally cools to room temperature after terminating；Then by the reaction product of gained
Washed out with tetrahydrofuran, by filtering can obtain tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane mixed liquor and
Residue, mixed liquor can obtain mixture by rotating solvent-recoverable；It is last to be obtained toward addition water sedimentation in mixture and filtering
The mixed solution of the mixed solution of rubber powder and ionic liquid and naphthane, ionic liquid and naphthane is reusable.By rubber powder
Weigh and calculate the yield of rubber powder.The yield of gained rubber powder is 52.8%.
Embodiment 4
Weigh 1g 1- butyl -3- methylimidazoles fluoroform sulphonate, 2ml naphthanes and 1g junked tire mix it is rearmounted
Vibrated in tubular type in kettle, react 2h at 100 DEG C.Reaction naturally cools to room temperature after terminating；Then by the reaction product of gained
Washed out with tetrahydrofuran, by filtering can obtain tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane mixed liquor and
Residue, mixed liquor can obtain mixture by rotating solvent-recoverable；It is last to be obtained toward addition water sedimentation in mixture and filtering
The mixed solution of the mixed solution of rubber powder and ionic liquid and naphthane, ionic liquid and naphthane is reusable.By rubber powder
Weigh and calculate the yield of rubber powder.The yield of gained rubber powder is 47.9%.
Embodiment 5
Weigh 1g 1- butyl -3- methylimidazoles fluoroform sulphonate, 2ml naphthanes and 1g junked tire mix it is rearmounted
Vibrated in tubular type in kettle, react 2h at 350 DEG C.Reaction naturally cools to room temperature after terminating；Then by the reaction product of gained
Washed out with tetrahydrofuran, by filtering can obtain tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane mixed liquor and
Residue, mixed liquor can obtain mixture by rotating solvent-recoverable；It is last to be obtained toward addition water sedimentation in mixture and filtering
The mixed solution of the mixed solution of rubber powder and ionic liquid and naphthane, ionic liquid and naphthane is reusable.By rubber powder
Weigh and calculate the yield of rubber powder.The yield of gained rubber powder is 54.2%.
Embodiment 6
Weigh 2g 1- butyl -3- methylimidazoles fluoroform sulphonate, 2ml naphthanes and 1g junked tire mix it is rearmounted
Vibrated in tubular type in kettle, react 2h at 200 DEG C.Reaction naturally cools to room temperature after terminating；Then by the reaction product of gained
Washed out with tetrahydrofuran, by filtering can obtain tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane mixed liquor and
Residue, mixed liquor can obtain mixture by rotating solvent-recoverable；It is last to be obtained toward addition water sedimentation in mixture and filtering
The mixed solution of the mixed solution of rubber powder and ionic liquid and naphthane, ionic liquid and naphthane is reusable.By rubber powder
Weigh and calculate the yield of rubber powder.The yield of gained rubber powder is 57.5%.
Embodiment 7
Weigh 5g 1- butyl -3- methylimidazoles fluoroform sulphonate, 20ml naphthanes and 1g junked tire mix after
It is placed in tubular type vibration kettle, reacts 2h at 250 DEG C.Reaction naturally cools to room temperature after terminating；Then the reaction of gained is produced
Thing is washed out with tetrahydrofuran, and the mixed liquor of tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane can be obtained by filtering
And residue, mixed liquor can obtain mixture by rotating solvent-recoverable；Finally can toward addition water sedimentation in mixture and filtering
Rubber powder and ionic liquid and naphthane mixed solution, the mixed solution of ionic liquid and naphthane is reusable.By glue
Powder is weighed and calculates the yield of rubber powder.The yield of gained rubber powder is 64.9%.
Embodiment 8
Weigh 0.1g 1- butyl -3- methylimidazoles fluoroform sulphonate, 1ml naphthanes and 1g junked tire mix after
It is placed in tubular type vibration kettle, is reacted at 400 DEG C after 0.5h reactions terminate and naturally cool to room temperature；Then the reaction of gained is produced
Thing is washed out with tetrahydrofuran, and the mixed liquor of tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane can be obtained by filtering
And residue, mixed liquor can obtain mixture by rotating solvent-recoverable；Finally can toward addition water sedimentation in mixture and filtering
Rubber powder and ionic liquid and naphthane mixed solution, the mixed solution of ionic liquid and naphthane is reusable.By glue
Powder is weighed and calculates the yield of rubber powder.The yield of gained rubber powder is 57.8%.
Embodiment 9
Weigh 1g 1- butyl -3- methylimidazoles fluoroform sulphonate, 1ml naphthanes and 1g junked tire mix it is rearmounted
Vibrated in tubular type in kettle, react 2h at 350 DEG C.Reaction naturally cools to room temperature after terminating；Then by the reaction product of gained
Washed out with tetrahydrofuran, by filtering can obtain tetrahydrofuran DDGS, tetrahydrofuran, ionic liquid and naphthane mixed liquor and
Residue, mixed liquor can obtain mixture by rotating solvent-recoverable；It is last to be obtained toward addition water sedimentation in mixture and filtering
The mixed solution of the mixed solution of rubber powder and ionic liquid and naphthane, ionic liquid and naphthane is reusable.By rubber powder
Weigh and calculate the yield of rubber powder.The yield of gained rubber powder is 59.6%.
Claims (2)
1. a kind of thermosol depolymerization junked tire is the method for rubber powder, it is characterised in that is comprised the following steps：
(1) junked tire, hydrogen supply dissolvent and ionic liquid are added to reactor, wherein ionic liquid, hydrogen supply dissolvent with it is waste and old
The mass ratio of tire is 0.1~5:1~20:1；
The ionic liquid is 1- butyl -3- methylimidazole fluoroform sulphonates；The hydrogen supply dissolvent is naphthane；
(2) the mixture heating that is formed the ionic liquid, hydrogen supply dissolvent and junked tire of step (1), temperature control are in room
Temperature~400 DEG C, reacts 0.5~4h, and reaction naturally cools to room temperature after terminating；
(3) reaction product obtained by step (2) is washed out with tetrahydrofuran, it is described mixed by being filtrated to get mixed liquor and residue
Liquid is closed by obtaining mixture after rotating recovery tetrahydrofuran；
(4) water sedimentation is added into the mixture of step (3) and is filtrated to get target product：Rubber powder.
2. a kind of thermosol depolymerization junked tire as claimed in claim 1 is the method for rubber powder, it is characterised in that the step
(1) mass ratio of intermediate ion liquid, hydrogen supply dissolvent and junked tire is 5:20:1；Mixture is heated in the step (2)
2h is reacted to 250 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510908326.9A CN105542817B (en) | 2015-12-07 | 2015-12-07 | A kind of thermosol depolymerization junked tire is the method for rubber powder |
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| CN201510908326.9A CN105542817B (en) | 2015-12-07 | 2015-12-07 | A kind of thermosol depolymerization junked tire is the method for rubber powder |
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| CN105542817B true CN105542817B (en) | 2018-03-02 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103525500A (en) * | 2013-10-28 | 2014-01-22 | 安徽工业大学 | Method for depolymerization of low-middle rank coal by cosolvent |
| CN104163937A (en) * | 2014-04-28 | 2014-11-26 | 安徽红太阳新材料有限公司 | Preparation method for promoting waste rubber reclaiming by using ionic liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9303134B2 (en) * | 2011-11-22 | 2016-04-05 | Ecosight, Llc | Recycling of solid waste in ionic liquid media |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103525500A (en) * | 2013-10-28 | 2014-01-22 | 安徽工业大学 | Method for depolymerization of low-middle rank coal by cosolvent |
| CN104163937A (en) * | 2014-04-28 | 2014-11-26 | 安徽红太阳新材料有限公司 | Preparation method for promoting waste rubber reclaiming by using ionic liquid |
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