CN111333905B - Recovery method of fiber reinforced composite material - Google Patents
Recovery method of fiber reinforced composite material Download PDFInfo
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- CN111333905B CN111333905B CN202010312567.8A CN202010312567A CN111333905B CN 111333905 B CN111333905 B CN 111333905B CN 202010312567 A CN202010312567 A CN 202010312567A CN 111333905 B CN111333905 B CN 111333905B
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- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000011084 recovery Methods 0.000 title abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000010438 heat treatment Methods 0.000 claims abstract description 80
- 239000000706 filtrate Substances 0.000 claims abstract description 55
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 52
- 239000000835 fiber Substances 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- 239000002028 Biomass Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 48
- 239000011148 porous material Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 24
- 238000003763 carbonization Methods 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 20
- 238000004064 recycling Methods 0.000 claims description 18
- 239000011964 heteropoly acid Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 11
- 239000002608 ionic liquid Substances 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 230000029936 alkylation Effects 0.000 claims description 5
- 238000005804 alkylation reaction Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000006277 sulfonation reaction Methods 0.000 claims description 4
- 238000011534 incubation Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002657 fibrous material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 229920000049 Carbon (fiber) Polymers 0.000 description 14
- 239000004917 carbon fiber Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000000197 pyrolysis Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229920002748 Basalt fiber Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000011208 reinforced composite material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- BZACCMFQBIWQCQ-UHFFFAOYSA-N 1,3-dimethyl-2H-imidazole trifluoromethanesulfonic acid Chemical compound CN1CN(C)C=C1.OS(=O)(=O)C(F)(F)F BZACCMFQBIWQCQ-UHFFFAOYSA-N 0.000 description 1
- AFSJUFFXOPXIOH-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound CC[NH+]1CN(C)C=C1.[O-]S(=O)(=O)C(F)(F)F AFSJUFFXOPXIOH-UHFFFAOYSA-N 0.000 description 1
- JASXXEXFHACUPE-UHFFFAOYSA-N 1-hexyl-3-methyl-2H-imidazole trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.CCCCCCN1CN(C)C=C1 JASXXEXFHACUPE-UHFFFAOYSA-N 0.000 description 1
- AKSIBPHQFIYJEY-UHFFFAOYSA-N 1-methyl-3-propyl-2H-imidazole trifluoromethanesulfonic acid Chemical compound FC(S(=O)(=O)O)(F)F.C(CC)N1CN(C=C1)C AKSIBPHQFIYJEY-UHFFFAOYSA-N 0.000 description 1
- PXKPKGHXANCVMC-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound OS(=O)(=O)C(F)(F)F.CCCCN1CN(C)C=C1 PXKPKGHXANCVMC-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
本发明涉及一种纤维增强复合材料的回收方法，所述方法包括如下步骤：(1)将纤维增强复合材料和酸混合并加热，之后固液分离，得到改性纤维和滤液；(2)对步骤(1)得到的滤液进行炭化处理，得到炭材料。本发明通过微波强化酸对纤维复合材料的树脂进行溶解并对纤维表面化学氧化处理，使树脂材料溶解于硫酸溶液中从而使纤维和树脂材料分离，得到纤维材料。本发明通过生物质或催化剂的作用下利用微波实现了纤维和树脂材料的全资源化回收，且较低的反应温度大幅度的降低了回收能耗，该方法路线短、操作简单、能耗低、适用范围广，具有重大的经济效益和环境效益。
The present invention relates to a method for recovering fiber-reinforced composite materials. The method comprises the following steps: (1) mixing and heating the fiber-reinforced composite material and acid, and then separating solid and liquid to obtain modified fibers and filtrate; (2) pairing The filtrate obtained in step (1) is carbonized to obtain carbon material. In the invention, the resin of the fiber composite material is dissolved by the microwave-reinforced acid and the surface of the fiber is chemically oxidized, so that the resin material is dissolved in the sulfuric acid solution to separate the fiber and the resin material to obtain the fiber material. The invention realizes the full resource recovery of fiber and resin material by using microwave under the action of biomass or catalyst, and the lower reaction temperature greatly reduces the energy consumption of recovery, the method has short route, simple operation and low energy consumption , A wide range of applications, with significant economic and environmental benefits.
Description
Technical Field
The invention relates to the field of waste resource utilization, in particular to a method for recycling a fiber reinforced composite material.
Background
Fiber Reinforced resin matrix composite (Fiber Reinforced Polymer, hereinafter abbreviated as FRP) has the advantages of light weight, high strength, high specific modulus, fatigue resistance, corrosion resistance, good designability and molding manufacturability and the like, and is widely applied in the fields of aerospace, sports equipment, wind power blades, building reinforcement, vehicles and the like.
The recovery method of the waste FRP mainly comprises physical recovery, energy recovery and chemical recovery. CN106750507A discloses a recovery method of a carbon fiber reinforced resin matrix composite material, which comprises the following steps: cutting the waste carbon fiber reinforced resin matrix composite into plates to obtain carbon fiber reinforced resin matrix composite plates, and then treating the resin on the surfaces of two ends of the obtained composite plates until the carbon fibers are exposed; then, carrying out aging treatment in electrolyte under the condition of ultrasonic reinforcement or microwave reinforcement; and connecting the exposed carbon fibers in the carbon fiber reinforced resin matrix composite plate obtained by aging treatment with the anode of a direct current power supply, connecting a graphite rod with the cathode of the direct current power supply, carrying out electrochemical reaction in electrolyte to obtain carbon fibers, and cleaning and drying the carbon fibers. The method improves the recovery efficiency of the carbon fiber, has no secondary pollution to the environment in the recovery process, and has small damage to the mechanical property of the recovered carbon fiber. CN108640699A discloses a method for preparing a carbon/carbon preform by recycling a carbon fiber reinforced resin-based composite material, which comprises the following steps: (1) carrying out pre-pyrolysis on the carbon fiber reinforced resin matrix composite material in an inert atmosphere to enable the composite material to generate holes and obtain a pre-pyrolysis product; (2) fully immersing the carbon increasing agent melt or the solution containing the carbon increasing agent into the holes of the pre-pyrolysis product, taking out and drying; (3) and (3) pyrolyzing the dried pre-pyrolysis product containing the carbon increasing agent in an inert atmosphere to fully convert the resin matrix into deposited carbon, so as to obtain the carbon/carbon preform. The carbon/carbon pre-forming body prepared by the method can be used for preparing carbon/carbon composite materials with high added values and carbon/ceramic composite materials, and the forward development and high-value reutilization of the carbon fiber reinforced resin matrix composite materials is realized.
But the existing fiber composite material has the problems of high energy consumption, low resin degradation rate, harsh reaction conditions, complex process and the like in the recovery process.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a method for recycling a fiber reinforced composite material, which realizes the full-resource recycling of fiber and resin materials, greatly reduces the recycling energy consumption at a lower reaction temperature, has a short route, is simple to operate, has low energy consumption and a wide application range, and has great economic and environmental benefits.
In order to achieve the purpose, the invention adopts the following technical scheme: the method comprises the following steps:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate;
(2) and (2) carrying out carbonization treatment on the filtrate obtained in the step (1) to obtain a carbon material.
The method comprises the steps of heating and dissolving resin of the fiber composite material by acid, carrying out chemical oxidation treatment on the surface of the fiber, and dissolving the resin material in an acid solution to separate the fiber from the resin material, thereby obtaining the fiber material. In the invention, the heating temperature is increased, the heating time is prolonged, the dissolution of the resin is facilitated, the oxidation reaction of the fiber and the sulfuric acid is also promoted, and the microwave can further strengthen the dissolution of the resin and the oxidation process of the fiber, thereby reducing the treatment time. However, too high a temperature and too long a time may reduce the fiber yield and the strength, and may partially char the resin. The resin is dissolved in acid to form waste sulfuric acid containing acid-soluble oil, and during the carbonization treatment of the waste sulfuric acid, biomass and a catalyst are added, so that the polymerization of the acid-soluble oil can be enhanced, more gas is generated during the reaction process, and the specific surface area of carbon is increased. The invention realizes the full recycling of fiber and resin materials by utilizing microwaves under the action of biomass or catalyst, greatly reduces the recycling energy consumption by lower reaction temperature, has short route, simple operation, low energy consumption and wide application range, and has great economic benefit and environmental benefit.
As a preferable technical scheme of the invention, the fiber reinforced composite material in the step (1) comprises 1 or at least 2 of carbon fiber reinforced composite material, glass fiber reinforced composite material or basalt fiber reinforced composite material.
As a preferred technical scheme of the invention, the acid in the step (1) comprises 1 or at least 2 of sulfuric acid, hydrochloric acid or nitric acid.
Preferably, the sulfuric acid comprises alkylation waste sulfuric acid and/or sulfonation waste sulfuric acid.
As a preferred embodiment of the present invention, the acid concentration in step (1) is not less than 30% by weight, and may be, for example, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 90% by weight, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the mass ratio of the fiber-reinforced composite material and the acid in the step (1) is 1 (1 to 100), and may be, for example, 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
As a preferable technical solution of the present invention, the heating method in the step (1) includes microwave heating.
Preferably, the power of the microwave heating is 1 to 500000W, and for example, 1W, 5W, 10W, 50W, 100W, 500W, 1kW, 2kW, 4kW, 6kW, 8kW, 10kW, 20kW, 30kW, 40kW, 50kW, 60kW, 70kW, 80kW, 90kW, 100kW, 150kW, 200kW, 250kW, 300kW, 350kW, 400kW, 450kW or 500kW, etc. may be mentioned, but not limited to the exemplified values, and other values not listed in the range are also applicable.
In a preferred embodiment of the present invention, the heating time in step (1) is 5 to 300min, for example, 5min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 120min, 140min, 160min, 180min, 200min, 220min, 240min, 260min, 280min, or 300min, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
Preferably, the heating temperature in step (1) is 50-300 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable technical solution of the present invention, the carbonization treatment in the step (2) is to add biomass and/or a catalyst to the filtrate, and then sequentially perform the first temperature rise and the second temperature rise.
Preferably, the amount of biomass added is 1 to 50% by mass of the filtrate, and may be, for example, 1%, 2%, 4%, 6%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% by mass, but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the catalyst is added in an amount of 0.01 to 5% by mass of the filtrate, for example, 0.01%, 0.02%, 0.04%, 0.06%, 0.08%, 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 2%, 3%, 4%, or 5%, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the catalyst comprises 1 or a combination of at least 2 of fluorosulfonic acid-based ionic liquids, sulfonic acid-based ionic liquids, acidic resins, supported phosphotungstic heteropoly acid catalysts, solid sulfonic acid catalysts, or cesium phosphotungstic heteropoly acid salt catalysts.
In the invention, the fluorosulfonic acid ionic liquid can be [ N ]222n1][MFn2]-TFSA、[N222n1][NTf2]-TFSA、[Cn1mim][DMMP]-TFSA or [ Cn1mim][MFn2]-TFSA (where M is P, B or Sb; n1 is 2, 4, 6 or 8; n2 is 4 or 6) and the like, such as 1, 3-dimethylimidazole trifluoromethanesulfonate, 1-ethyl-3-methylimidazole trifluoromethanesulfonate, 1-propyl-3-methylimidazole trifluoromethanesulfonate, 1-butyl-3-methylimidazole trifluoromethanesulfonate, 1-hexyl-3-methylimidazole trifluoromethanesulfonate.
In the invention, the cation of the sulfonic acid ionic liquid is imidazole, quaternary ammonium salt and pyridine, and the anion is hydrogen sulfate which can be [ C ]n1mim][MFn2]-H2SO4、[N222n1][MFn2]-H2SO4、[Cn1Py][MFn2]-H2SO4(wherein M-P, B or Sb; n-1-2, 4, 6 or 8; n-2-4 or 6) and the like.
In the present invention, the acidic resin may be an acidic cation adsorbent resin, an acidic anion adsorbent resin, a perfluorosulfonic acid resin or the like
In the invention, the supported phosphotungstic heteropoly acid catalyst can be activated carbon supported phosphotungstic heteropoly acid, molecular sieve supported phosphotungstic heteropoly acid or SiO2Oxide-supported phosphotungstic heteropoly acid, and the like.
In the invention, the solid sulfonic acid catalyst can be biomass sulfonated carbon material or benzene sulfonate and the like
In the invention, the cesium phosphotungstic heteropoly acid salt catalyst can be a clay-supported cesium phosphotungstic heteropoly acid salt catalyst or an activated carbon-supported cesium phosphotungstic heteropoly acid salt catalyst and the like.
Preferably, the end point temperature of the first temperature rise is 120-160 ℃, for example, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃ or 160 ℃, etc., but not limited to the enumerated values, and other unrecited values within the range are also applicable.
The holding time after the first temperature rise is preferably 0.5 to 3 hours, and may be, for example, 0.5 hour, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, or 3 hours, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the end point temperature of the second temperature rise is 170-190 ℃, and may be, for example, 170 ℃, 172 ℃, 174 ℃, 176 ℃, 178 ℃, 180 ℃, 182 ℃, 184 ℃, 186 ℃, 188 ℃ or 190 ℃, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the incubation time after the first temperature rise is 0.5 to 5 hours, for example, 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5 hours, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
As a preferred embodiment of the present invention, the matrix resin of the fiber-reinforced composite material includes a thermosetting resin and/or a thermoplastic resin.
Preferably, the product obtained by the carbonization treatment in the step (2) further comprises sulfur dioxide.
Preferably, the sulfur dioxide is oxidized to obtain sulfur trioxide and sulfuric acid.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite material comprises 1 or a combination of at least 2 of a carbon fiber-reinforced composite material, a glass fiber-reinforced composite material or a basalt fiber-reinforced composite material; the acid comprises 1 or a combination of at least 2 of sulfuric acid, hydrochloric acid or nitric acid; the sulfuric acid comprises alkylation waste sulfuric acid and/or sulfonation waste sulfuric acid; the mass concentration of the acid is more than or equal to 30 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1 (1-100); the heating mode comprises microwave heating; the power of the microwave heating is 1-500000W; the heating time is 5-300 min; the heating temperature is 50-300 ℃; the matrix resin of the fiber-reinforced composite material includes a thermosetting resin and/or a thermoplastic resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; wherein the carbonization treatment comprises the steps of adding biomass and/or a catalyst into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the biomass is 1-50% of the mass of the filtrate; the adding amount of the catalyst is 0.01-5% of the mass of the filtrate; the catalyst comprises 1 or at least 2 of fluorosulfonic acid ionic liquid, sulfonic acid ionic liquid, acidic resin, supported phosphotungstic heteropoly acid catalyst, solid sulfonic acid catalyst or cesium phosphotungstic heteropoly acid catalyst; the end temperature of the first temperature rise is 120-160 ℃; the heat preservation time after the first temperature rise is 0.5-3 h; the end temperature of the second temperature rise is 170-190 ℃; the heat preservation time after the first temperature rise is 0.5-5 h; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
Compared with the prior art, the invention has the following beneficial effects:
the method realizes the full-resource recovery of the fiber and resin materials, greatly reduces the recovery energy consumption by a lower reaction temperature, has short route, simple operation, low energy consumption and wide application range, and has great economic benefit and environmental benefit. The specific surface area of the obtained carbon material can reach 500m at most2G, pore diameter of 1.5-2.3nm, pore volume of 60-180mm3/g。
Drawings
FIG. 1 is a scanning electron micrograph of a modified fiber obtained in example 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The present embodiment provides a method for recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite material comprises a carbon fiber-reinforced composite material; the acid is sulfuric acid; the mass concentration of the acid is 98 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1: 27.17; the heating mode comprises microwave heating; the power of the microwave heating is 20W; the heating time is 20 min; the heating temperature is 100 ℃; the matrix resin of the fiber-reinforced composite material includes a thermosetting resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; wherein the carbonization treatment comprises the steps of adding biomass (rice hull) into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the biomass is 20% of the mass of the filtrate; the end point temperature of the first temperature rise is 140 ℃; the heat preservation time after the first temperature rise is 2 hours; the end point temperature of the second temperature rise is 180 ℃; the heat preservation time after the first temperature rise is 4 hours; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
The scanning electron micrograph of the obtained modified fiber is shown in FIG. 1; the mass recovery rate of the obtained modified fiber, and the specific surface, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Example 2
The present embodiment provides a method for recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite comprises a glass fiber-reinforced composite; the acid is alkylation waste sulfuric acid; the mass concentration of the acid is 88.2 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1: 24.27; the heating mode comprises microwave heating; the power of the microwave heating is 100W; the heating time is 10 min; the heating temperature is 200 ℃; the matrix resin of the fiber-reinforced composite material includes a thermosetting resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; wherein the carbonization treatment comprises the steps of adding biomass (rice hull) into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the biomass is 20% of the mass of the filtrate; the end point temperature of the first temperature rise is 160 ℃; the heat preservation time after the first temperature rise is 1.5 h; the end point temperature of the second temperature rise is 170 ℃; the heat preservation time after the first temperature rise is 3.5 hours; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
The mass recovery rate of the obtained modified fiber, and the specific surface, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Example 3
The present embodiment provides a method for recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite material comprises a basalt fiber-reinforced composite material; the acid is sulfuric acid; the mass concentration of the acid is 65 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1: 14.39; the heating mode comprises microwave heating; the microwave heating power is 800W; the heating time is 300 min; the heating temperature is 50 ℃; the matrix resin of the fiber-reinforced composite material includes a thermoplastic resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; adding a catalyst into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the catalyst is 3% of the mass of the filtrate; the catalyst is a molecular sieve supported phosphotungstic heteropoly acid catalyst; the end point temperature of the first temperature rise is 155 ℃; the heat preservation time after the first temperature rise is 1 h; the end point temperature of the second temperature rise is 190 ℃; the heat preservation time after the first temperature rise is 4 hours; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
The mass recovery rate of the obtained modified fiber, and the specific surface, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Example 4
The present embodiment provides a method for recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite material comprises a carbon fiber-reinforced composite material; the acid is sulfonated waste sulfuric acid; the mass concentration of the acid is 80 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1: 90; the heating mode comprises microwave heating; the power of the microwave heating is 200 kW; the heating time is 5 min; the heating temperature is 300 ℃; the matrix resin of the fiber-reinforced composite material includes a thermoplastic resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; adding a catalyst into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the catalyst is 5% of the mass of the filtrate; the catalyst comprises fluorosulfonic acid ionic liquid; the end point temperature of the first temperature rise is 160 ℃; the heat preservation time after the first temperature rise is 3 hours; the end point temperature of the second temperature rise is 190 ℃; the heat preservation time after the first temperature rise is 4 hours; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
The mass recovery rate of the obtained modified fiber, and the specific surface, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Example 5
The present embodiment provides a method for recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber reinforced composite comprises a basalt fiber reinforced composite; the acid is alkylation waste sulfuric acid and sulfonation waste sulfuric acid; the mass concentration of the acid is 85 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1: 5; the heating mode comprises microwave heating; the power of the microwave heating is 100 kW; the heating time is 20 min; the heating temperature is 60 ℃; the matrix resin of the fiber-reinforced composite material includes a thermosetting resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; wherein the carbonization treatment comprises the steps of adding biomass (coconut shells) into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the biomass is 5% of the mass of the filtrate; the end point temperature of the first temperature rise is 130 ℃; the heat preservation time after the first temperature rise is 2 hours; the end point temperature of the second temperature rise is 170 ℃; the heat preservation time after the first temperature rise is 5 hours; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
The mass recovery rate of the obtained modified fiber, and the specific surface, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Example 6
The present embodiment provides a method for recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite material comprises a carbon fiber-reinforced composite material; the acid is sulfuric acid; the mass concentration of the acid is 65 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1: 60; the heating mode comprises microwave heating; the power of the microwave heating is 10 kW; the heating time is 60 min; the heating temperature is 70 ℃; the matrix resin of the fiber-reinforced composite material includes a thermoplastic resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; wherein the carbonization treatment comprises adding biomass (reed stems) into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the biomass is 30% of the mass of the filtrate; the end point temperature of the first temperature rise is 140 ℃; the heat preservation time after the first temperature rise is 3 hours; the end point temperature of the second temperature rise is 190 ℃; the heat preservation time after the first temperature rise is 5 hours; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
The mass recovery rate of the obtained modified fiber, and the specific surface, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Example 7
The present embodiment provides a method for recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite material comprises a carbon fiber-reinforced composite material; the acid comprises sulfuric acid; the mass concentration of the acid is 98 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1: 100; the heating mode comprises electric heating; the power of the electric heating is 10 kW; the heating time is 180 min; the heating temperature is 120 ℃; the matrix resin of the fiber-reinforced composite material includes a thermoplastic resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; adding a catalyst into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the catalyst is 0.01 percent of the mass of the filtrate; the catalyst comprises activated carbon supported cesium phosphotungstic heteropoly acid salt; the end point temperature of the first temperature rise is 140 ℃; the heat preservation time after the first temperature rise is 2 hours; the end point temperature of the second temperature rise is 190 ℃; the heat preservation time after the first temperature rise is 1 h; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
The mass recovery rate of the obtained modified fiber, and the specific surface, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Example 8
The present embodiment provides a method for recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite comprises a glass fiber-reinforced composite; the acid is sulfuric acid and nitric acid with the mass ratio of 8: 2; the mass concentration of the sulfuric acid is 88.2 wt%, and the concentration of the nitric acid is 60%; the mass ratio of the fiber reinforced composite material to the acid is 1: 71; the heating mode comprises microwave heating; the power of the microwave heating is 1 KW; the heating time is 50 min; the heating temperature is 150 ℃; the matrix resin of the fiber-reinforced composite material includes a thermosetting resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; wherein the carbonization treatment comprises the steps of adding biomass (rice hull) into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the biomass is 20% of the mass of the filtrate; the end point temperature of the first temperature rise is 160 ℃; the heat preservation time after the first temperature rise is 1.5 h; the end point temperature of the second temperature rise is 170 ℃; the heat preservation time after the first temperature rise is 3.5 hours; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
The mass recovery rate of the obtained modified fiber, and the specific surface, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Comparative example 1
The only difference from example 1 is that the heating time is 1min, the mass recovery rate of the obtained modified fiber, and the specific surface area, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Comparative example 2
The only difference from example 1 is that the heating time is 500min, the mass recovery rate of the obtained modified fiber, and the specific surface area, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Comparative example 3
The only difference from example 1 is that the heating temperature is 30 ℃, the mass recovery rate of the obtained modified fiber, and the specific surface area, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Comparative example 4
The only difference from example 1 is that the heating temperature is 330 ℃, the mass recovery rate of the obtained modified fiber, and the specific surface area, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Comparative example 5
The only difference from example 1 is that instead of microwave heating, water bath heating is used instead, the mass recovery rate of the obtained modified fiber, and the specific surface area, pore diameter and pore volume of the obtained carbon material are detailed in table 1.
Comparative example 6
The only difference from example 1 is that no biomass is added, the mass recovery of the resulting modified fiber, and the specific surface, pore size and pore volume of the resulting carbon material are detailed in table 1.
Comparative example 7
The only difference from example 3 is that the mass recovery of the modified fiber obtained without adding catalyst, and the specific surface area, pore diameter and pore volume of the carbon material obtained are detailed in table 1.
TABLE 1 modified fiber recovery and Performance parameters of the resulting carbon materials in the examples and comparative examples
| Percent recovery% | Specific surface area/m2/g | Pore size/nm | Pore volume/mm3/g | |
| Example 1 | 99.6 | 264.2 | 2.1 | 130 |
| Example 2 | 99.1 | 280 | 1.8 | 150 |
| Example 3 | 99.1 | 260 | 2.3 | 120 |
| Example 4 | 99.8 | 240 | 1.5 | 130 |
| Example 5 | 99.3 | 300 | 1.7 | 160 |
| Example 6 | 98.5 | 290 | 1.6 | 180 |
| Example 7 | 99.5 | 500 | 1.6 | 175 |
| Example 8 | 99.2 | 230 | 1.8 | 150 |
| Comparative example 1 | 54.1 | 200 | 2.2 | 128 |
| Comparative example 2 | 93.7 | 64 | 2.1 | 184 |
| Comparative example 3 | 60.5 | 202 | 1.4 | 178 |
| Comparative example 4 | 72.6 | 119.3 | 1.4 | 54 |
| Comparative example 5 | 81.9 | 149.2 | 0.9 | 81 |
| Comparative example 6 | 99.5 | 120 | 3.4 | 260 |
| Comparative example 7 | 98.5 | 150 | 2.7 | 240 |
The results of the above examples and comparative examples show that the invention realizes the full recycling of fiber and resin materials by using microwaves under the action of biomass or catalysts, and the lower reaction temperature greatly reduces the recycling energy consumption.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (18)
1. A method of recycling a fiber-reinforced composite material, the method comprising the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; the heating mode is microwave heating; the power of the microwave heating is 1-500000W; the heating time is 5-300 min; the heating temperature is 50-300 ℃;
(2) carbonizing the filtrate obtained in the step (1) to obtain the filtrate with the maximum specific surface area of 500m2G, pore diameter of 1.5-2.3nm, pore volume of 60-180mm3Carbon material per gram.
2. The method of claim 1, wherein the fiber-reinforced composite of step (1) comprises 1 or a combination of at least 2 of a carbon fiber-reinforced composite, a glass fiber-reinforced composite, or a basalt fiber-reinforced composite.
3. The method of claim 1, wherein the acid of step (1) comprises 1 or a combination of at least 2 of sulfuric acid, hydrochloric acid, or nitric acid.
4. The method of claim 3, wherein the sulfuric acid comprises alkylated spent sulfuric acid and/or sulfonated spent sulfuric acid.
5. The method according to claim 1, wherein the mass concentration of the acid in the step (1) is not less than 30 wt%.
6. The method of claim 1, wherein the mass ratio of the fiber-reinforced composite material and the acid in the step (1) is 1 (1-100).
7. The method according to claim 1, wherein the carbonization treatment in the step (2) is to add biomass and/or a catalyst to the filtrate, and then sequentially perform the first temperature rise and the second temperature rise.
8. The method of claim 7, wherein the biomass is added in an amount of 1-50% by mass of the filtrate.
9. The method of claim 7, wherein the catalyst is added in an amount of 0.01 to 5% by mass of the filtrate.
10. The method of claim 7, wherein the catalyst comprises 1 or a combination of at least 2 of fluorosulfonic acid-based ionic liquids, sulfonic acid-based ionic liquids, acidic resins, supported phosphotungstic heteropoly acid catalysts, solid sulfonic acid catalysts, or cesium phosphotungstic heteropoly acid salt catalysts.
11. The method as claimed in claim 7, wherein the end point temperature of the first temperature rise is 120-160 ℃.
12. The method of claim 7, wherein the incubation time after the first temperature increase is from 0.5 to 3 hours.
13. The method as claimed in claim 7, wherein the end temperature of the second temperature rise is 170-190 ℃.
14. The method of claim 7, wherein the hold time after the first temperature increase is from 0.5 to 5 hours.
15. The method of claim 1, wherein the matrix resin of the fiber-reinforced composite material comprises a thermosetting resin and/or a thermoplastic resin.
16. The method of claim 1, wherein the product of the carbonization treatment of step (2) further comprises sulfur dioxide.
17. The process of claim 16, wherein the sulfur dioxide is oxidized to produce sulfur trioxide and sulfuric acid.
18. The method of claim 1, wherein the method comprises the steps of:
(1) mixing and heating the fiber reinforced composite material and acid, and then carrying out solid-liquid separation to obtain modified fiber and filtrate; wherein the fiber-reinforced composite material comprises 1 or a combination of at least 2 of a carbon fiber-reinforced composite material, a glass fiber-reinforced composite material, or a basalt fiber-reinforced composite material; the acid comprises 1 or a combination of at least 2 of sulfuric acid, hydrochloric acid or nitric acid; the sulfuric acid comprises alkylation waste sulfuric acid and/or sulfonation waste sulfuric acid; the mass concentration of the acid is more than or equal to 30 wt%; the mass ratio of the fiber reinforced composite material to the acid is 1 (1-100); the heating mode comprises microwave heating; the power of the microwave heating is 1-500000W; the heating time is 5-300 min; the heating temperature is 50-300 ℃; the matrix resin of the fiber-reinforced composite material includes a thermosetting resin and/or a thermoplastic resin;
(2) carbonizing the filtrate obtained in the step (1) to obtain a carbon material; wherein the carbonization treatment comprises the steps of adding biomass and/or a catalyst into the filtrate, and then sequentially carrying out first temperature rise and second temperature rise; the adding amount of the biomass is 1-50% of the mass of the filtrate; the adding amount of the catalyst is 0.01-5% of the mass of the filtrate; the catalyst comprises 1 or at least 2 of fluorosulfonic acid ionic liquid, sulfonic acid ionic liquid, acidic resin, supported phosphotungstic heteropoly acid catalyst, solid sulfonic acid catalyst or cesium phosphotungstic heteropoly acid catalyst; the end temperature of the first temperature rise is 120-160 ℃; the heat preservation time after the first temperature rise is 0.5-3 h; the end temperature of the second temperature rise is 170-190 ℃; the heat preservation time after the first temperature rise is 0.5-5 h; the product obtained by the carbonization treatment also comprises sulfur dioxide; and oxidizing the sulfur dioxide to obtain sulfur trioxide and sulfuric acid.
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