CN102181071B - Method for reclaiming carbon fiber reinforced epoxy resin composite material - Google Patents
Method for reclaiming carbon fiber reinforced epoxy resin composite material Download PDFInfo
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- CN102181071B CN102181071B CN2011101020032A CN201110102003A CN102181071B CN 102181071 B CN102181071 B CN 102181071B CN 2011101020032 A CN2011101020032 A CN 2011101020032A CN 201110102003 A CN201110102003 A CN 201110102003A CN 102181071 B CN102181071 B CN 102181071B
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 39
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 238000004821 distillation Methods 0.000 claims abstract description 19
- 239000012265 solid product Substances 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003930 superacid Substances 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019253 formic acid Nutrition 0.000 claims abstract description 5
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000000354 decomposition reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 229940027987 antiseptic and disinfectant phenol and derivative Drugs 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007867 post-reaction treatment Methods 0.000 description 2
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Reinforced Plastic Materials (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a method for reclaiming a carbon fiber reinforced epoxy resin composite material. The conventional method is high in equipment requirement and high in reclamation cost. The method comprises the following steps of: adding a catalyst into an organic reagent to prepare supercritical CO2 composite solution; putting the carbon fiber reinforced epoxy resin composite material to be decomposed into a reaction kettle, and adding the supercritical CO2 composite solution; and reacting for 1 to 24 hours at the temperature of between 100 and 250 DEG C under the pressure of 7.5 to 25.0MPa, cooling the product to normal temperature, washing and drying the solid product in the product to obtain carbon fibers, and performing reduced pressure distillation on the liquid product in the product to obtain phenol and derivatives thereof. The catalyst is one or two of liquid super acid, solid super acid, phosphotungstic acid, phosphomolybdic acid, acetic acid, formic acid, hydrochloric acid, sulfuric acid and nitric acid. The method has the advantages of high degradation efficiency, environmental friendliness, low cost and the like, and is a green method for reclaiming the waste and old carbon fiber reinforced epoxy resin composite material.
Description
Technical field
The invention belongs to polymer recovery technology field, relate to a kind of method that reclaims waste and old same with thermosetting compound material, relate in particular to a kind of method of utilizing overcritical complex liquid to reclaim carbon-fibre reinforced epoxy resin composite material.
Background technology
Carbon fiber (CF))/Resins, epoxy (EP) matrix material (be called for short CF/EP matrix material) has that density is little, specific tenacity and specific modulus all have the wide application of sending out than higher characteristics, particularly carbon fiber/epoxy resin composite material at high-technology fields such as aviation field, automotive industry, sports goodss.Along with the development of low-carbon economy, carbon fiber/epoxy resin composite material is at the consumption rapid growth of every field, and constantly is extended to emerging field as new forms of energy, bullet train etc.Along with the application of carbon fiber/epoxy resin composite material in these high frontiers, the thermosetting resin junk that produces grows with each passing day, brought huge pressure to environment on the one hand, the carbon fiber composition that contains high value on the other hand in the matrix material, if matrix material is simply handled, will cause the waste of resource.
At present, the research to thermoset ting resin composite also is in the starting stage, bright the lacking of method of energy high efficiente callback carbon fiber/epoxy resin composite material.Traditional method is difficult to reclaim efficiently matrix material: burning can only the recovery part heat, but has produced the gas of some poisonous easy contaminate environment in the burning process; Elevated temperature heat degraded (Thermochimica Acta454 (2007): 109-115) be recovered to clean filler and fortifying fibre, but need to carry out under the higher temperature of reaction, conversion unit is had relatively high expectations; Fluidized-bed (Applied Surface Science254 (2008) 2588 – 2593) needs higher temperature just can be recovered to clean carbon fiber equally; And liquid-phase pyrolysis method (Polymer Degradation and Stability89 (2005) 317-326) is owing to use a large amount of organic solvents in the removal process, may to environment produce pollute and cost recovery higher; Because the lower acid resistance of Resins, epoxy, utilize nitric acid (Journal of Applied Polymer Science, Vol.95,1912 – 1916 (2004)), severe corrosive acid such as formic acid can degrade to Resins, epoxy, the recyclable carbon fiber that obtains surface clean, but strong acid such as nitric acid are because corrodibility is strong, to having relatively high expectations of conversion unit, and the operational safety coefficient is had relatively high expectations, and cost recovery is higher, and post-reaction treatment is difficult; Be considered to have the overcritical flowing water (Materials and Design31 (2010) 999 – 1002) of bright prospects though have the characteristics of cleanliness without any pollution, but also need under the reaction conditions of High Temperature High Pressure, carry out, and product and water after the degraded mix, and is not easily separated; Supercritical alcohols fluids such as (Ind.Eng.Chem.Res.2010,49,4535 – 4541) was also all realized the degraded to Resins, epoxy afterwards, but also was in laboratory stage at present, also had a segment distance from real industrialization.
Summary of the invention
The method that the purpose of this invention is to provide a kind of high efficiente callback carbon-fibre reinforced epoxy resin, this method has that resin degradation rate height, environmental friendliness, cost are low, the characteristics such as reusable edible of resource, can remedy and be difficult to high efficiente callback carbon fiber, post-reaction treatment complexity, be difficult to realize defectives such as suitability for industrialized production.
The inventive method is with supercritical CO
2Be environment, add complex liquid, under relatively mild condition, realize the degraded of carbon-fibre reinforced epoxy resin composite material, and the control reaction conditions makes its product produce with phenol and homologue thereof, thereby the realization carbon fiber separates with Resins, epoxy, specifically may further comprise the steps:
Step (1) preparation complex liquid, concrete grammar is: catalyzer is added in the organic reagent, stir, make complex liquid; Every liter of organic reagent adds 5～100 gram catalyzer.
Described organic solvent is ethanol, acetone, n-propyl alcohol, propyl carbinol, N, one or both in dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), chloroform, the methyl-sulphoxide;
Described catalyzer is one or both in liquid superacid, solid super-strong acid, phospho-wolframic acid, phospho-molybdic acid, acetic acid, formic acid, hydrochloric acid, sulfuric acid, the nitric acid;
Described liquid superacid is a kind of in chlorsulfonic acid, the trifluoromethayl sulfonic acid;
Described solid super-strong acid is SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ Fe
2O
3, SO
4 2-/ TiO
2-ZrO
2A kind of in the type super acids.
Step (2) is put into reactor with the carbon-fibre reinforced epoxy resin composite material of required decomposition, adds complex liquid then, and the carbon-fibre reinforced epoxy resin composite material of the required decomposition of per 100 grams adds 0.5～5.0 liter of complex liquid.
Step (3) charges into CO after reactor is vacuumized then
2Gas reacted 1～24 hour under 100～250 ℃, the above-critical state of 7.5～25.0MPa, naturally cooled to normal temperature then, obtained elementary product.
Step (4) with the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
The inventive method is with supercritical CO
2Be environment, add organic reagent commonly used and catalyzer composition supercritical CO
2The complex liquid system impels matrix material under comparatively gentle condition, is degraded into phenol and homologue thereof and is dissolved in supercritical CO
2In the complex liquid system, thereby the recovery separately of realization carbon fiber and Resins, epoxy realizes the resource circulation utilization, has alleviated the pressure of thermoset ting resin composite to environment to a certain extent.The inventive method has advantages such as the degradation efficiency height, environmental friendliness, low cost of Resins, epoxy, is a kind of green method that reclaims waste and old carbon-fibre reinforced epoxy resin composite material.Be embodied as:
The carbon fiber surface resin that recovery obtains is almost residual; The degradation rate of Resins, epoxy reaches more than 95% in the carbon fiber/epoxy resin;
The intensity of the carbon fiber that recovery obtains is more than 90% of pristine fibre, can be combined into matrix material again with Resins, epoxy;
The degradable component of carbon fiber/epoxy resin is based on phenol and homologue thereof, can reuse through can be used as industrial chemicals etc. after the fractionation by distillation;
Reaction back CO
2Easily from reactor, separate reusable edible.
In addition, the present invention can realize reacting under low-temp low-pressure, and reaction has the reaction conditions gentleness, easy control of reaction conditions, and reaction medium and catalyzer can be recycled, and by product is less, is pollution-free basically, equipment is not had advantages such as corrosion.
Embodiment
Below in conjunction with example the present invention is further specified:
Embodiment 1:
With 1.0 * 10
-4Rise (1.7 * 10
-3Mole) acetic acid and 0.02 gram SO4
2-/ ZrO
2Add 1.95 * 10
-2Rise (0.25 mole) N, in the dinethylformamide, stir, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 15 hours under 120 ℃, the above-critical state of 12MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 2:
With 6.2 * 10
-4Rise (5.9 * 10
-3Mole) 30% hydrochloric acid adds 8.1 * 10
-3Rise (8.9 * 10
-2Mole) in the propyl carbinol, stirs, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 5.5 hours under 180 ℃, the above-critical state of 8MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 3:
With 2.0 * 10
-4Rise (2.3 * 10
-3Mole) trifluoromethayl sulfonic acid adds 5.2 * 10
-3Rise (7.1 * 10
-2Mole) in the acetone, stirs, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 7 hours under 220 ℃, the above-critical state of 7.5MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 4:
Be 10% phosphotungstic acid aqueous solution (9.2 * 10 with 0.265 gram mass mark
-6Mole) adds 5.3 * 10
-3Rise (9.1 * 10
-2Mole) in the ethanol, stirs, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 24 hours under 105 ℃, the above-critical state of 20MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 5:
With 5.0 * 10
-4Rise (1.3 * 10
-2Mole) formic acid adds 6.1 * 10
-3Rise (7.5 * 10
-2Mole) in the tetrahydrofuran (THF), stirs, make and close liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 10 hours under 100 ℃, the above-critical state of 25MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 6:
Be 5% phospho-molybdic acid water (2.7 * 10 with 1.0 gram mass marks
-5Mole) solution adds 6.2 * 10
-3Rise (8.3 * 10
-2) in the n-propyl alcohol, stir, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 16 hours under 165 ℃, the above-critical state of 14MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 7:
With 2.0 * 10
-4Rise (3.7 * 10
-3Mole) 98% sulfuric acid adds 7.5 * 10
-3(0.11 mole) rises in the methyl-sulphoxide, stirs, and makes complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 1 hour under 250 ℃, the above-critical state of 18MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 8:
With 0.05 gram SO
4 2-/ TiO
2Solid super-strong acid adds 5.3 * 10
-3Rise (5.7 * 10
-2Mole) in the N,N-dimethylacetamide, stirs, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 4.5 hours under 145 ℃, the above-critical state of 12MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 9:
With 1.0 * 10
-4Rise (1.5 * 10
-3Mole) chlorsulfonic acid adds 2.5 * 10
-3Rise (3.1 * 10
-2Mole) in the chloroform, stirs, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 22 hours under 110 ℃, the above-critical state of 13MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 10:
With 0.08 gram SO
4 2-/ TiO
2-ZrO
2Solid super-strong acid adds 1.0 * 10
-3Rise (1.1 * 10
-2Mole) N,N-dimethylacetamide and 1.0 * 10
-3Rise (1.3 * 10
-5Mole) N in the dinethylformamide, stirs, and makes complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 2.5 hours under 135 ℃, the above-critical state of 23MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 11:
With 0.07 gram SO
4 2-/ Fe
2O
3Solid super-strong acid adds 1.5 * 10
-3Rise (2.0 * 10
-2Mole) acetone and 2.0 * 10
-3Rise (3.4 * 10
-2Mole) in the ethanol, stirs, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 5.5 hours under 200 ℃, the above-critical state of 11.5MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 12:
With 3.0 * 10
-4Rise (4.7 * 10
-3Mole) 70% nitric acid adds 6.5 * 10
-3(9.2 * 10
-2Mole) rises in the methyl-sulphoxide, stir, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 3.5 hours under 145 ℃, the above-critical state of 20MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 13:
With 2.5 * 10
-4Rise (4.4 * 10
-3Mole) acetic acid adds 6.5 * 10
-3(8.4 * 10
-2Mole) rises N, in the dinethylformamide, stir, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 21 hours under 190 ℃, the above-critical state of 10MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 14:
With 0.3 gram SO
4 2-/ TiO
2With 0.02 gram SO
4 2-/ Fe
2O
3Solid super-strong acid adds 1.0 * 10
-3Rise (1.1 * 10
-2Mole) N,N-dimethylacetamide and 8.5 * 10
-3Rise in (0.11 mole) n-propyl alcohol, stir, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 4.5 hours under 185 ℃, the above-critical state of 7MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Embodiment 15:
With 0.2 gram SO
4 2-/ ZrO
2Solid super-strong acid adds 1.4 * 10
-2Rise in (0.15 mole) propyl carbinol, stir, make complex liquid; The carbon-fibre reinforced epoxy resin composite material of the required decomposition of 0.4 gram is put into reactor, add the complex liquid of having prepared then; Reactor is vacuumized, charge into CO then
2Gas, reaction is 8 hours under 205 ℃, the above-critical state of 17MPa, naturally cools to normal temperature then, obtains elementary product; With the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
Claims (4)
1. method that reclaims carbon-fibre reinforced epoxy resin composite material is characterized in that the concrete steps of this method are:
Step (1) preparation complex liquid, concrete grammar is: catalyzer is added in the organic reagent, stir, make complex liquid; Add 5～100 gram catalyzer in every liter of organic reagent;
Described catalyzer is one or both in liquid superacid, solid super-strong acid, phospho-wolframic acid, phospho-molybdic acid, acetic acid, formic acid, hydrochloric acid, sulfuric acid, the nitric acid;
Described organic solvent is ethanol, acetone, n-propyl alcohol, propyl carbinol, N, one or both in dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), chloroform, the methyl-sulphoxide;
Step (2) is put into reactor with the carbon-fibre reinforced epoxy resin composite material of required decomposition, adds complex liquid then;
Step (3) vacuumizes reactor, charges into CO then
2Gas reacted 1～24 hour under 100～250 ℃, the above-critical state of 7.5～25.0MPa, naturally cooled to normal temperature then, obtained elementary product;
Step (4) with the solid product in the elementary product wash, the dry carbon fiber that obtains; Product liquid in the elementary product is carried out underpressure distillation obtain the phenol derivmives blend biology.
2. a kind of method that reclaims carbon-fibre reinforced epoxy resin composite material as claimed in claim 1, it is characterized in that: the liquid superacid described in the step (1) is chlorsulfonic acid or trifluoromethayl sulfonic acid.
3. a kind of method that reclaims carbon-fibre reinforced epoxy resin composite material as claimed in claim 1, it is characterized in that: the solid super-strong acid described in the step (1) is SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ Fe
2O
3, SO
4 2-/ TiO
2-ZrO
2A kind of in the type super acids.
4. a kind of method that reclaims carbon-fibre reinforced epoxy resin composite material as claimed in claim 1 is characterized in that: 0.5～5.0 liter of complex liquid of carbon-fibre reinforced epoxy resin composite material adding of the required decomposition of per 100 grams in the step (2).
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| CN102558603B (en) * | 2012-01-13 | 2014-04-16 | 同济大学 | Method for one-step recovery and modification of carbon fiber |
| CN104662074B (en) * | 2012-07-19 | 2018-01-09 | 英派尔科技开发有限公司 | Using solvent cracking carbon fiber is recycled from epoxy resin |
| CN102888750B (en) * | 2012-10-29 | 2014-03-12 | 哈尔滨工业大学 | Method for modifying surface of carbon fiber |
| CN103333360B (en) * | 2013-07-10 | 2015-07-01 | 合肥工业大学 | Reinforcement mode based high-performance fiber reinforced resin based composite material recovery method |
| CN103483554B (en) | 2013-09-24 | 2015-12-02 | 艾达索高新材料无锡有限公司 | Degradable hydrazone based epoxy resin curing agent and application thereof |
| CN103694140B (en) * | 2013-12-02 | 2016-09-28 | 艾达索高新材料无锡有限公司 | Degradable isocyanate and application thereof |
| CN104327303B (en) * | 2014-11-11 | 2017-02-01 | 合肥工业大学 | Supercritical fluid recovery device and method of carbon-fiber-reinforced resin-base composite material |
| CN105482154A (en) * | 2015-12-16 | 2016-04-13 | 华东理工大学 | Method for recycling carbon fibers from carbon-fiber-enhanced high polymer material based on induction heating effect |
| CN105906836A (en) * | 2016-05-09 | 2016-08-31 | 西北工业大学 | Recovering method of carbon fiber reinforced resin matrix composite material under mild conditions |
| CN106957451B (en) | 2017-04-01 | 2019-09-10 | 北京化工大学 | A method of recycling carbon fiber from discarded carbon fiber resin matrix composite |
| CN108640699B (en) * | 2018-04-28 | 2020-10-27 | 中国人民解放军国防科技大学 | Method for preparing carbon/carbon preformed body by recycling carbon fiber reinforced resin matrix composite material |
| CN109384415B (en) * | 2018-09-18 | 2021-03-02 | 科之杰新材料集团有限公司 | Preparation method of concrete anti-cracking reinforcing agent |
| CN109518264B (en) * | 2018-11-09 | 2020-03-10 | 深圳大学 | Electro-catalysis heterogeneous catalysis recovery device based on CFRP material and control method thereof |
| CN111471214B (en) * | 2019-01-23 | 2022-07-29 | 纳米及先进材料研发院有限公司 | Method for recycling epoxy molding compound waste |
| CN111363197A (en) * | 2020-03-11 | 2020-07-03 | 中国大唐集团科学技术研究院有限公司火力发电技术研究院 | Method for recovering thermosetting fiber composite material by supercritical fluid |
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