CN117025274B - Method for preparing solid fuel by using waste carbon fiber wind power blades - Google Patents
Method for preparing solid fuel by using waste carbon fiber wind power blades Download PDFInfo
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- CN117025274B CN117025274B CN202311291468.6A CN202311291468A CN117025274B CN 117025274 B CN117025274 B CN 117025274B CN 202311291468 A CN202311291468 A CN 202311291468A CN 117025274 B CN117025274 B CN 117025274B
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- carbon fiber
- wind power
- waste carbon
- fiber wind
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 118
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 118
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000002699 waste material Substances 0.000 title claims abstract description 93
- 239000004449 solid propellant Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003607 modifier Substances 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000002791 soaking Methods 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- 150000007522 mineralic acids Chemical group 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000011162 core material Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 150000003841 chloride salts Chemical class 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/40—Solid fuels essentially based on materials of non-mineral origin
- C10L5/48—Solid fuels essentially based on materials of non-mineral origin on industrial residues and waste materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/22—Impregnation or immersion of a fuel component or a fuel as a whole
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/24—Mixing, stirring of fuel components
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/28—Cutting, disintegrating, shredding or grinding
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention relates to the field of solid waste treatment, and discloses a method for preparing solid fuel by using waste carbon fiber wind power blades. The method comprises the following steps: (1) Pretreating waste carbon fiber wind power blades to obtain crushed waste carbon fiber wind power blades; (2) Soaking crushed waste carbon fiber wind power blades in an organic solvent, and then carrying out solid-liquid separation; (3) Mixing the obtained solid phase with a solution containing a modifier for reaction, then mixing a reaction product with a binder, and then extruding and molding; (4) carrying out heat treatment on the material obtained in the step (3). The method can realize the recycling treatment of the waste carbon fiber wind power blade, and the waste carbon fiber wind power blade is used for preparing the solid fuel, so that the prepared solid fuel has high heat value and high combustion rate, and has a wide industrial application prospect.
Description
Technical Field
The invention relates to the field of solid waste treatment, in particular to a method for preparing solid fuel by using waste carbon fiber wind power blades.
Background
Wind power generation is an important low-carbon development mode, the wind power generation industry in China is greatly developed, the demand for wind power generation materials is more and more increased, and wind power blades are the most important components in wind turbine generator materials. However, the wind turbine generator materials have service length, and the decommissioned wind turbine generator materials face the problems of recycling and the like. The types of wind power blades commonly used at present are glass fiber wind power blades and carbon fiber wind power blades, and the carbon fiber wind power blades are mainly used for offshore wind power generation. The carbon fiber wind power blade is a composite material of carbon fiber and resin, and is difficult to carry out post-treatment due to difficult degradation and the like, and the recovery mode of the waste carbon fiber wind power blade commonly used at present adopts a thermal cracking method and the like to recover the waste carbon fiber wind power blade, but the thermal cracking reaction is usually carried out under the conditions of higher temperature and pressure, the recovery condition is more severe, and the waste carbon fiber wind power blade cannot be completely recovered, so that a method capable of completely realizing resource utilization of the waste carbon fiber wind power blade is needed to be searched.
At present, the solid fuel prepared by utilizing the solid waste generally has the problems of low combustion efficiency, low heat value and the like, and the market application of the solid fuel is greatly restricted by the defects.
Disclosure of Invention
The invention aims to solve the problems that the recycling recovery of waste carbon fiber wind power blades is difficult, the waste carbon fiber wind power blades cannot be fully recovered, the heat value of the existing solid fuel is low and the like in the prior art, and provides a method for preparing the solid fuel by utilizing the waste carbon fiber wind power blades.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing solid fuel using waste carbon fiber wind power blades, the method comprising the steps of:
(1) Pretreating waste carbon fiber wind power blades to obtain crushed waste carbon fiber wind power blades;
(2) Placing the crushed waste carbon fiber wind power blades into an organic matter for soaking, and then carrying out solid-liquid separation;
(3) Mixing the solid phase obtained by solid-liquid separation in the step (2) with a solution containing a modifier for reaction, mixing a reaction product with a binder, and then extruding and molding;
(4) Carrying out heat treatment on the material obtained in the step (3);
wherein the modifier is selected from inorganic acid, hydroxide or chloride;
preferably, when the modifier is an inorganic acid, H in the solution containing the modifier + Concentration of (2)0.05-4mol/L;
and/or the hydroxide is selected from one or more than two of NaOH, KOH and ammonia water;
and/or the chloride salt is selected from NaCl, znCl 2 And MgCl 2 One or two or more of them.
Preferably, the organic matter is selected from C 1 -C 4 Fatty alcohols and/or C 3 -C 5 Aliphatic ketone.
Preferably, in step (3), the reaction conditions include: the temperature is 110-150 ℃ and the time is 2-12h.
Preferably, in step (2), the soaking conditions include: the temperature is 90-120 ℃ and the time is 30-200min;
and/or the liquid-solid ratio of the soaking is 2-15 mL/1 g.
Preferably, the conditions of the heat treatment include: the temperature is 500-600deg.C, and the time is 20-150min.
Preferably, when the modifier is an inorganic acid, the concentration of the modifier in the modifier-containing solution is 0.05 to 4mol/L;
and/or, when the modifier is a hydroxide, the mass concentration of the modifier in the solution containing the modifier is 1-20%;
and/or, when the modifier is chloride salt, the concentration of the modifier in the solution containing the modifier is 0.2mol/L to 4mol/L.
Preferably, the solid-to-liquid ratio of the crushed waste carbon fiber wind power blade materials to the solution containing the modifier is 1g:7-20mL.
Preferably, the particle size of the crushed waste carbon fiber wind power blade is less than or equal to 80 meshes.
Preferably, the binder is one or more selected from the group consisting of polyvinyl alcohol, polytetrafluoroethylene and polyolefin;
and/or the weight ratio of the binder to the amount of the crushed waste carbon fiber wind power blade is 5-13:100.
Preferably, the waste carbon fiber wind power blade contains 55-85wt% of carbon fiber, 10-30wt% of resin and 0.5-15% of core material.
In the method, firstly, the waste carbon fiber wind power blades are pretreated, then the pretreated crushed aggregates are soaked in an organic solvent, resin and carbon fibers in the waste carbon fiber wind power blades become more loose and porous, then the soaked materials are mixed with a modifier for reaction, and the carbon fibers in the waste carbon fiber wind power blades are activated, so that the carbon fibers and the resin in the waste carbon fiber wind power blades are both changed into inflammable substances, and then the materials are further loosened through heat treatment, so that the prepared solid fuel can be more fully contacted with oxygen for combustion in the application process. According to the method, the waste carbon fiber wind power blade is used for preparing the solid fuel, so that the recycling of the waste carbon fiber wind power blade is realized, the carbon fiber and the resin in the waste carbon fiber wind power blade are recycled, and the prepared solid fuel is high in heat value and high in combustion rate, so that the application range of the solid fuel is further expanded.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the invention, the method for preparing the solid fuel by using the waste carbon fiber wind power blade comprises the following steps:
(1) Pretreating waste carbon fiber wind power blades to obtain crushed waste carbon fiber wind power blades;
(2) Placing the crushed waste carbon fiber wind power blades into an organic matter for soaking, and then carrying out solid-liquid separation;
(3) Mixing the solid phase obtained by solid-liquid separation in the step (2) with a solution containing a modifier for reaction, mixing a reaction product with a binder, and then extruding and molding;
(4) And (3) carrying out heat treatment on the material obtained in the step (3).
In the method of the invention, the main components of the waste carbon fiber wind power blade are carbon fibers, resin and core materials, and the rest components are less. The carbon fibers and the resin contained in the waste carbon fiber wind power blade are interwoven and are difficult to separate, and the content of the carbon fibers in the waste carbon fiber wind power blade is 55-85wt% of carbon fibers, 10-30wt% of resin and 0.5-15% of core material in the waste carbon fiber wind power blade.
In the method of the present invention, in step (1), the pretreatment process may be a pretreatment step common in the art. Preferably, the pretreatment process comprises: cutting the waste carbon fiber wind power blades, and grinding to obtain crushed waste carbon fiber wind power blades. In particular, the milling may be performed by wet ball milling, which may be performed according to a method common in the art.
In a preferred embodiment, the particle size of the crushed waste carbon fiber wind power blades is less than or equal to 80 meshes, preferably 100-200 meshes.
In the method, the crushed aggregates of the waste carbon fiber wind power blades are placed in the organic matters for soaking, so that the resin in the waste carbon fiber wind power blades can be promoted to contain more holes, the solid fuel prepared later can be conveniently combusted in contact with oxygen, and the full fuel and the combustion efficiency of the prepared solid fuel are ensured.
In a preferred embodiment, the organic matter is selected from C in order to further enhance the combustion efficiency of the solid fuel produced 1 -C 4 Fatty alcohols and/or C 3 -C 5 Aliphatic ketone. More preferably, the organic matter is selected fromFrom C 1 -C 4 Fatty alcohols or C 3 -C 5 Aliphatic ketone. Specifically, the C1-C4 fatty alcohol can be one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol and glycerol; the C3-C5 aliphatic ketone can be one or more of acetone, butanone and pentanone.
In a preferred embodiment, the organic is selected from methanol or acetone.
In a preferred embodiment, in step (2), the soaking conditions include: the temperature is 90-120deg.C, and the time is 30-200min, preferably 60-120min. Specifically, the soaking temperature may be 90 ℃, 100 ℃, 110 ℃ or 120 ℃; the soaking time can be 60min, 90min or 120min.
In a preferred embodiment, in step (2), the soaking has a liquid to solid ratio of 2-15mL:1g, preferably 5-10mL:1g.
In the prior art, carbon fibers and resin contained in the waste carbon fiber wind power blade are interwoven, wherein the carbon fibers are limited by the existence form of the carbon fibers in the waste carbon fiber wind power blade, so that the carbon fibers are difficult to burn. Meanwhile, gaps between the resin and the carbon fibers in the material after the material is reacted with the modifier are enlarged, the original interweaving structure of the carbon fibers and the resin in the waste carbon fiber wind power blade is broken, the whole material is loose, the soaked material can be broken, the combustion heat value of the prepared solid fuel is further improved, and the combustion efficiency of the solid fuel is further improved. And the resin contained in the waste carbon fiber wind power blade has certain adhesive property after reacting with the modifier, so that the prepared solid fuel is easy to solidify and shape, and meanwhile, the strength of the solid fuel after shaping can be improved, and the solid fuel is not easy to loosen too much when in use.
According to the method, the waste carbon fiber wind power blade is treated, the resin and the carbon fiber in the waste carbon fiber wind power blade are all used for preparing the solid fuel, and the heat value and the combustion rate of the prepared solid fuel are further improved.
In the method of the present invention, the modifier is selected from inorganic acids, hydroxides or chloride salts.
In a preferred embodiment, the inorganic acid is selected from one or more of phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.
In a preferred embodiment, to avoid reducing the combustion heating value of the solid fuel produced, when the modifier is a mineral acid, H is present in the solution containing the modifier + The concentration of (C) is 0.05-4mol/L, preferably 1-3mol/L.
In a preferred embodiment, the hydroxide is selected from one or more of NaOH, KOH and aqueous ammonia.
In a preferred embodiment, the chloride salt is selected from NaCl, znCl 2 And MgCl 2 One or two or more of them.
In a specific embodiment, the solution containing the modifying agent may be obtained by dissolving the modifying agent in water.
In a preferred embodiment, when the modifier is an inorganic acid, the concentration of the modifier in the solution containing the modifier is 0.05 to 4mol/L, preferably 1 to 3mol/L. Specifically, the concentration of the modifier may be 0.05mol/L, 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, or 4mol/L.
In a preferred embodiment, when the modifier is a hydroxide, the mass concentration of the modifier in the solution containing the modifier is 1 to 20%, preferably 10 to 18%. Specifically, the concentration of the modifier may be 1%, 5%, 10%, 15% or 20%.
In a preferred embodiment, when the modifier is a chloride salt, the concentration of the modifier in the solution containing the modifier is 0.2 to 4mol/L, preferably 2.5 to 3.5mol/L. Specifically, the concentration of the modifier may be 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, or 4mol/L.
In the preferred embodiment, in order to further improve the combustion heat value of the prepared solid fuel and ensure that the solid fuel can be fully combusted, in the step (3), the solid-to-liquid ratio of the crushed waste carbon fiber wind power blade materials to the solution containing the modifier is 1g:7-20mL. Specifically, the solid-to-liquid ratio of the crushed waste carbon fiber wind power blade to the solution containing the modifier may be 1g:7mL, 1g:10mL, 1g:15mL or 1g:20mL.
In a preferred embodiment, the hydrothermal reaction conditions include: the temperature is 110-150 ℃ and the time is 2-12h.
In the method of the invention, the binder is used for facilitating the shaping of the solid fuel, and the binder is one or more selected from polyvinyl alcohol, polytetrafluoroethylene and polyolefin. Preferably, the polyolefin is selected from polyethylene and/or polypropylene.
In a preferred embodiment, the weight ratio of the binder to the amount of the crushed waste carbon fiber wind power blade material is 5-13:100, preferably 6-12:100. Specifically, the weight ratio of the binder to the amount of the crushed waste carbon fiber wind power blades may be 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100 or 13:100.
In the method of the present invention, in the step (3), the extrusion temperature at the time of extrusion molding is 120 to 250 ℃.
In the method of the present invention, the heat treatment conditions include: the temperature is 500-600deg.C, and the time is 20-150min, preferably 40-120min. Specifically, the temperature of the heat treatment is 500 ℃, 550 ℃ or 600 ℃; the heat treatment time is 20min, 40min, 60min, 100min, 120min or 150min. According to the invention, the material after extrusion molding is subjected to heat treatment, so that the abundant holes in the obtained solid fuel are further ensured, and the prepared solid fuel can be fully combusted.
In a specific embodiment, the atmosphere during the heat treatment may be a protective atmosphere such as nitrogen, argon or helium.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The experimental methods in the following examples and comparative examples, unless otherwise specified, are conventional in the art. The experimental materials used in the following examples and comparative examples are commercially available unless otherwise specified.
Wherein the binder is polyvinyl alcohol, purchased from Shanghai Ala Biochemical technology Co., ltd, and the product name is polyvinyl alcohol 1788 type.
Example 1
(1) Cutting waste carbon fiber wind power blades (the resin content is 21.68wt%, the core material content is 1.45 wt%, and the carbon fiber content is 76.87 wt%) and then ball milling to obtain waste carbon fiber wind power blade crushed aggregates (the particle size is less than or equal to 100 meshes);
(2) Soaking the crushed waste carbon fiber wind power blades in acetone at a temperature of 100 ℃ for 80min, wherein the liquid-solid ratio during soaking is 5 mL/1 g; filtering after soaking;
(3) Mixing the filter residue obtained by filtering with a sodium hydroxide aqueous solution (the mass concentration of NaOH in the sodium hydroxide aqueous solution is 15wt%, the liquid-solid ratio of the sodium hydroxide aqueous solution to the consumption of the crushed waste carbon fiber wind power blades is 10mL:1 g), and then carrying out a reaction at 120 ℃ for 6 hours; mixing the obtained reaction product with a binder (polyvinyl alcohol) after the reaction is finished, then extruding and molding, wherein the extruding temperature is 150 ℃, and then drying the material obtained by the extruding and molding at 80 ℃ for 2 hours; wherein the weight ratio of the binder polyvinyl alcohol to the amount of the crushed aggregates of the waste carbon fiber wind power blades is 7.5:100;
(4) And (3) carrying out heat treatment on the dried material in the step (3) in a nitrogen atmosphere, wherein the heat treatment temperature is 500 ℃, the time is 60 minutes, and the solid fuel can be obtained after the heat treatment is finished.
Example 2
(1) Cutting waste carbon fiber wind power blades (resin content is 26.43wt%, core material content is 2.07% and carbon fiber content is 71.5 wt%) and then ball milling to obtain waste carbon fiber wind power blade crushed aggregates (particle size is less than or equal to 100 meshes);
(2) Soaking the crushed waste carbon fiber wind power blades in acetone at 110 ℃ for 90min, wherein the liquid-solid ratio during soaking is 6.5 mL/1 g; filtering after soaking;
(3) Mixing the filtered filter residue with an ammonia water solution (the mass concentration of the ammonia water solution is 15%, the liquid-solid ratio of the ammonia water solution to the amount of the waste carbon fiber wind power blade crushed aggregates is 9mL:1 g), and then carrying out reaction at the temperature of 150 ℃ for 5h; mixing the obtained reaction product with a binder (polyvinyl alcohol) after the reaction is finished, then extruding and molding, wherein the extruding temperature is 150 ℃, and then drying the material obtained by the extruding and molding at 80 ℃ for 2 hours; wherein the weight ratio of the binder polyvinyl alcohol to the amount of the crushed aggregates of the waste carbon fiber wind power blades is 10:100;
(4) And (3) carrying out heat treatment on the dried material in the step (3) in a nitrogen atmosphere, wherein the heat treatment temperature is 520 ℃, the time is 60 minutes, and the solid fuel can be obtained after the heat treatment is finished.
Example 3
(1) Cutting waste carbon fiber wind power blades (resin content is 20.38wt%, core material content is 0.98% carbon fiber content is 78.64 wt%) and then ball milling to obtain waste carbon fiber wind power blade crushed aggregates (particle size is less than or equal to 100 meshes);
(2) Soaking the crushed waste carbon fiber wind power blades in acetone at the temperature of 120 ℃ for 90min, wherein the liquid-solid ratio during soaking is 6.5 mL/1 g; filtering after soaking;
(3) Mixing the filter residue obtained by filtering with an aqueous NaCl solution (the concentration of NaCl in the aqueous NaCl solution is 3mol/L, the liquid-solid ratio of the aqueous NaCl solution to the amount of crushed waste carbon fiber wind power blades is 12mL:1 g), and then reacting at 150 ℃ for 6 hours; mixing the obtained reaction product with a binder (polyvinyl alcohol) after the reaction is finished, then extruding and molding, wherein the extruding temperature is 150 ℃, and then drying the material obtained by the extruding and molding at 80 ℃ for 2 hours; wherein, the weight ratio of the polyvinyl alcohol to the consumption of the crushed aggregates of the waste carbon fiber wind power blades is 11:100;
(4) And (3) carrying out heat treatment on the dried material in the step (3) in an argon atmosphere, wherein the heat treatment temperature is 550 ℃, the time is 50 minutes, and the solid fuel can be obtained after the heat treatment is finished.
Example 4
(1) Cutting waste carbon fiber wind power blades (resin content is 29.99wt%, core material content is 1.56% carbon fiber content is 68.45 wt%) and then ball milling to obtain waste carbon fiber wind power blade crushed aggregates (particle size is less than or equal to 100 meshes);
(2) Soaking the crushed waste carbon fiber wind power blades in acetone at the temperature of 120 ℃ for 90min, wherein the liquid-solid ratio during soaking is 6.5 mL/1 g; filtering after soaking;
(3) The residue obtained by filtration was combined with HCl solution (H in HCl solution) + The concentration of the solution is 2mol/L, the liquid-solid ratio of the HCl solution to the amount of the crushed waste carbon fiber wind power blades is 8.8 mL:1g), and the solution is mixed for reaction, wherein the reaction temperature is 140 ℃ and the reaction time is 6h; mixing the obtained reaction product with a binder (polyvinyl alcohol) after the reaction is finished, then extruding and molding, wherein the extruding temperature is 150 ℃, and then drying the material obtained by the extruding and molding at 80 ℃ for 2 hours; wherein, the weight ratio of the polyvinyl alcohol to the consumption of the crushed aggregates of the waste carbon fiber wind power blades is 10:100;
(4) And (3) carrying out heat treatment on the dried material in the step (3) in an argon atmosphere, wherein the heat treatment temperature is 550 ℃, the time is 50 minutes, and the solid fuel can be obtained after the heat treatment is finished.
Comparative example 1
The method of example 4 was performed, except that step (2) was not performed, and the crushed aggregates of the waste carbon fiber wind power blades were directly mixed with HCl solution to react.
Comparative example 2
The procedure of example 4 was followed, except that step (3) was not performed, and the residue obtained by filtration in step (2) was mixed with a binder and then extruded.
Comparative example 3
The procedure of example 4 was followed except that no binder was added.
Comparative example 4
The procedure of example 4 was followed except that the heat treatment in step (4) was not performed.
Comparative example 5
The procedure of example 4 was followed, except that the modifier was NaNO 3 。
Test case
Test example 1
The solid fuels prepared in the examples and comparative examples were tested for performance parameters.
Heating value of solid fuel: carrying out heat measurement by using an oxygen bomb calorimeter (model XRY-1A), measuring each sample three times, taking the average value of the three experiments as measurement data, and the results are shown in table 1;
compressive strength: placing a sample to be tested on a flat plate of a pressure testing machine by using an electronic universal testing machine (model ZWICK/Instron 5969), applying pressure at a constant speed, measuring the maximum pressure born during crushing, measuring each sample in parallel for three times, taking the average value of the three times as measurement data, and obtaining the results shown in Table 1;
specific surface area: the specific surface area of the sample to be measured was measured by mercury intrusion detector (model number: mike AutoPore 9500), and the results are shown in table 1;
TABLE 1
As can be seen from the results in Table 1, the method disclosed by the invention is used for preparing the solid fuel by using the waste carbon fiber wind power blade, and the prepared solid fuel has high heat value, high compressive strength and specific surface, namely, not only realizes the recycling utilization of the waste carbon fiber wind power blade, but also opens up the preparation way of the solid fuel.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The method for preparing the solid fuel by using the waste carbon fiber wind power blade is characterized by comprising the following steps of:
(1) Pretreating waste carbon fiber wind power blades to obtain crushed waste carbon fiber wind power blades;
(2) Placing the crushed waste carbon fiber wind power blades into an organic matter for soaking, and then carrying out solid-liquid separation;
(3) Mixing the solid phase obtained by solid-liquid separation in the step (2) with a solution containing a modifier for reaction, mixing a reaction product with a binder, and then extruding and molding;
(4) Carrying out heat treatment on the material obtained in the step (3);
wherein the modifier is selected from inorganic acid, hydroxide or chloride;
the organic matter is selected from C 1 -C 4 Fatty alcohols and/or C 3 -C 5 Aliphatic ketone;
in step (2), the soaking conditions include: the temperature is 90-120 ℃ and the time is 30-200min;
in step (3), the reaction conditions include: the temperature is 110-150 ℃ and the time is 2-12h;
when the modifier is an inorganic acid, H in the solution containing the modifier + The concentration of (2) is 0.05-4mol/L;
the hydroxide is selected from one or more than two of NaOH, KOH and ammonia water;
the chloride salt is selected from NaCl, znCl 2 And MgCl 2 One or two or more of them.
2. The method for preparing solid fuel by utilizing waste carbon fiber wind power blades according to claim 1, wherein the soaking liquid-solid ratio is 2-15 mL/1 g.
3. The method for preparing solid fuel by using waste carbon fiber wind power blades according to claim 1, wherein the heat treatment conditions comprise: the temperature is 500-600deg.C, and the time is 20-150min.
4. The method for preparing solid fuel by using waste carbon fiber wind power blades according to claim 1, wherein when the modifier is inorganic acid, the concentration of the modifier in the solution containing the modifier is 0.05-4mol/L.
5. The method for preparing solid fuel by using waste carbon fiber wind power blades according to claim 1, wherein when the modifier is hydroxide, the mass concentration of the modifier in the solution containing the modifier is 1-20%.
6. The method for preparing solid fuel by using waste carbon fiber wind power blades according to claim 1, wherein when the modifier is chloride salt, the concentration of the modifier in the solution containing the modifier is 0.2mol/L-4mol/L.
7. The method for preparing solid fuel by using waste carbon fiber wind power blades according to any one of claims 4 to 6, wherein the solid-to-liquid ratio of the crushed waste carbon fiber wind power blades to the solution containing the modifier is 1g:7-20mL.
8. The method for preparing solid fuel by using waste carbon fiber wind power blades according to claim 1, wherein the binder is one or more selected from the group consisting of polyvinyl alcohol, polytetrafluoroethylene and polyolefin.
9. The method for preparing solid fuel by utilizing waste carbon fiber wind power blades according to claim 1, wherein the weight ratio of the binder to the amount of crushed waste carbon fiber wind power blades is 5-13:100.
10. The method for preparing solid fuel by using waste carbon fiber wind power blades according to claim 1, wherein the waste carbon fiber wind power blades comprise 55-85wt% of carbon fiber, 10-30wt% of resin and 0.5% -15% of core material.
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