CN116274288B - Method for recycling waste wind power blades - Google Patents
Method for recycling waste wind power blades Download PDFInfo
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- CN116274288B CN116274288B CN202310556529.0A CN202310556529A CN116274288B CN 116274288 B CN116274288 B CN 116274288B CN 202310556529 A CN202310556529 A CN 202310556529A CN 116274288 B CN116274288 B CN 116274288B
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- 239000002699 waste material Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- 239000003365 glass fiber Substances 0.000 claims abstract description 101
- 238000001354 calcination Methods 0.000 claims abstract description 90
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000002791 soaking Methods 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 238000012216 screening Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000005520 cutting process Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000003929 acidic solution Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002817 coal dust Substances 0.000 claims description 4
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/75—Plastic waste
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of solid waste treatment, and discloses a method for recycling waste wind power blades, which comprises the following steps: (1) Cutting waste wind power blades into blocks, crushing the blocks, and collecting crushed aggregates with the particle size of 0.5-10 mm; (2) Calcining the crushed aggregates obtained in the step (1) in the first stage, soaking a calcined product in an acid solution, filtering, and washing and drying filter residues to obtain a material S; (3) Mixing the material S with a roasting additive, then carrying out second-stage calcination, screening the calcined product, and collecting crushed aggregates with the particle size of 0.425-20 mm; (4) And (3) calcining the crushed aggregates obtained in the step (3) in a third stage. The method disclosed by the invention not only can carry out resource treatment on the waste wind power blades, but also can recycle the waste wind power blades to obtain the glass fiber products with higher commercial value and wider application range of subsequent products.
Description
Technical Field
The invention relates to the field of solid waste treatment, in particular to a method for recycling waste wind power blades.
Background
Wind power is a clean renewable energy source, and wind power generation is an important path for green development at present. With the rapid development of wind power generation, a large number of wind turbine generator systems are put into use. The wind power blade is an important part of the wind turbine generator, but the service time of the wind power blade is about 20 years, so that a large number of decommissioned or damaged wind power blades face a series of recovery treatment and other problems along with large-area popularization of wind power generation. The wind power blade commonly used at present is mainly made of a composite material of glass fiber and resin, wherein the glass fiber is an inorganic nonmetallic material with excellent performance, and has the advantages of good insulativity, strong heat resistance, good corrosion resistance, high mechanical strength and the like. Since glass fibers are stacked in a bundle form and resin layers in wind power blades and are difficult to peel off, most of the current methods for recovering glass fibers in waste wind power blades directly crush waste wind power blades and recover the crushed waste wind power blades, and control of the form of the recovered glass fibers is not paid attention to. However, in the prior art, the strength of the glass fiber obtained by directly crushing and recycling the waste wind power blades is greatly lost, the application value of the subsequently obtained glass fiber product is greatly reduced, and the purity of the recycled glass fiber is low and the application range is narrow. And certain waste still exists for the low recovery rate of glass fiber.
In addition, although the scope of industrial application of the glass fibers in a bundle is wider, the glass fibers in a bundle are extremely fragile during the disposal of waste wind turbine blades, and thus it is extremely difficult to maintain the form of the glass fibers during the recovery.
Disclosure of Invention
The invention aims to solve the problems that the waste wind power blade is difficult to recycle, and the recycled glass fiber is low in strength, purity and yield and difficult to maintain the original form of the glass fiber in the prior art. The method disclosed by the invention not only can carry out resource treatment on the waste wind power blades, but also can recycle the waste wind power blades to obtain the glass fiber products which are excellent in strength performance, higher in commercial value and wider in application range of subsequent products.
In order to achieve the above purpose, the invention provides a method for recycling waste wind power blades, which comprises the following steps:
(1) Cutting waste wind power blades into blocks, crushing the blocks, and collecting crushed aggregates with the particle size of 0.5-10 mm;
(2) Calcining the crushed aggregates obtained in the step (1) in the first stage, soaking a calcined product in an acid solution, filtering, and washing and drying filter residues to obtain a material S;
(3) Mixing the material S with a roasting additive, then carrying out second-stage calcination, screening the calcined product, and collecting crushed aggregates with the particle size of 0.425-20 mm;
(4) And (3) calcining the crushed aggregates obtained in the step (3) in a third stage.
Preferably, the block is a cuboid, the width of the cuboid is 1-4cm, the length of the cuboid is 1-20cm, and the height of the cuboid is 2-20cm.
Preferably, the conditions of the first stage calcination include: the temperature is 200-250deg.C, and the time is 5-10min.
Preferably, the conditions of the second stage calcination include: the temperature is 300-450 ℃ and the time is 10-30min.
Preferably, the conditions of the third stage calcination include: the temperature is 250-450 ℃ and the time is 5-8min.
Preferably, the acidic solution is selected from acetic acid solution and/or hydrochloric acid solution.
Preferably, the concentration of solute in the acidic solution is 0.3-3mol/L.
Preferably, in step (2), the soaking conditions include: the temperature is 80-110 ℃ and the time is 20-60min.
Preferably, in the step (2), the liquid-solid ratio during soaking is 10-20 mL/1 g.
Preferably, the calcination additive is selected from carbon powder and/or coal dust.
Preferably, the weight ratio of the roasting additive to the amount of the material S is 1:5-30.
Preferably, the waste wind power blade contains 52-76wt% of glass fiber and 24-48wt% of resin.
The method disclosed by the invention not only can carry out resource treatment on the waste wind power blades, but also can recycle the waste wind power blades to obtain the glass fiber products with higher commercial value and wider application range. According to the method for recycling the waste wind power blade, the waste wind power blade is cut into a plurality of small blocks in advance, then the small blocks are cut and crushed, the damage to the form of glass fibers in the waste wind power blade caused by the crushing process is avoided, and then the three-stage calcination is further carried out, the calcination temperature and the calcination time are controlled, so that the resin in the waste wind power blade can be effectively removed, and meanwhile, a single bundled glass fiber product can be obtained. More importantly, the glass fiber recovered by the recovery method has high purity, the purity of the glass fiber can reach 97-98%, the strength of the original glass fiber is well maintained while the high-purity glass fiber product is recovered, the strength performance of the recovered glass fiber product is 96-97% of that of the original glass fiber raw material, the glass fiber product recovered by the method is a single bundle-shaped glass fiber, the glass fibers are rarely adhered, and compared with the glass fiber powder product recovered by the conventional technology, the glass fiber powder product has higher commercial value and application prospect.
Drawings
FIG. 1 is a graph of the macroscopic morphology of the recycled glass fiber product of this example 2.
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.
The invention provides a method for recycling waste wind power blades, which comprises the following steps:
(1) Cutting waste wind power blades into blocks, crushing the blocks, and collecting crushed aggregates with the particle size of 0.5-10 mm;
(2) Calcining the crushed aggregates obtained in the step (1) in the first stage, soaking a calcined product in an acid solution, filtering, and washing and drying filter residues to obtain a material S;
(3) Mixing the material S with a roasting additive, then carrying out second-stage calcination, screening the calcined product, and collecting crushed aggregates with the particle size of 0.425-20 mm;
(4) And (3) calcining the crushed aggregates obtained in the step (3) in a third stage.
In the method of the invention, the waste wind power blade refers to a wind power blade which is out of service or damaged due to failure, the main components of the waste wind power blade are glass fiber and resin (the content of the rest components is very small and can be ignored, and the property of the waste wind power blade is not greatly different from the main components), and the waste wind power blade contains 52-76wt% of glass fiber and 24-48wt% of resin, preferably 55-75wt% of glass fiber and 25-45wt% of resin. In the untreated waste wind power blade, the glass fibers are laminated with the resin in a bundle shape, and the glass fibers can be recovered on the basis of not damaging the original glass fiber shape by adopting the method disclosed by the invention, so that single glass fibers in the bundle shape are obtained, the strength performance loss is extremely low, and the method has high commercial value.
In the method disclosed by the invention, in the step (1), the waste wind power blade is firstly cut into a plurality of small blocks, and then the small blocks are crushed, so that the situation that the waste wind power blade is directly crushed to cause serious damage to the form of glass fibers in the waste wind power blade is avoided, and the integrity of the form of the finally recovered glass fibers is maintained.
In a specific embodiment, in step (1), it is necessary to crush all the obtained blocks at the time of crushing.
In the method of the present invention, each of the blocks may be a rectangular parallelepiped, a square, a cone, or an irregularly shaped block, and the specific shape of the block is not limited.
In a specific embodiment, in the step (1), the number of blocks obtained by cutting is greater than or equal to 150.
In a preferred embodiment, each of the blocks is a rectangular parallelepiped, each of which has a width of 1 to 4cm, a length of 1 to 20cm, and a height of 2 to 20cm. In the present invention, the size relationship among the length, width and height of the rectangular parallelepiped is not limited, and for example, the length of the rectangular parallelepiped is not necessarily required to be larger than the width or height. Specifically, the width of the rectangular parallelepiped may be 1cm, 2cm, 3cm, or 4cm; the length may be 1cm, 5cm, 10cm, 12cm, 15cm, 18cm or 20cm; the height may be 2cm, 5cm, 8cm, 10cm, 15cm or 20cm.
In a further preferred embodiment, the cuboid has a width of 1-4cm, a length of 4-18cm and a height of 2-15cm.
According to the method, the sizes of the blocks obtained by cutting the waste wind power blades are limited, so that the recovery rate of the glass fibers can be further improved, and the purity of the finally recovered glass fibers can be improved.
In a preferred embodiment, the particle size of the crushed aggregates finally collected in step (1) is controlled to be 0.5-6mm in order to further maintain the integrity of the shape of the recovered glass fibers. In particular, the particle size of the chaff a may be 0.5mm, 2mm, 4mm, 6mm, 7mm, 9mm or 10mm.
In a further preferred embodiment, in step (1), in order to further control the crushing degree of the waste wind power blades, the ratio of crushed aggregates having a particle diameter of 100 mesh or less in the crushed aggregates obtained after crushing is controlled to be 0.5 to 10wt%.
In a specific embodiment, in step (1), crushed aggregates with a particle size of 0.5-10mm can be collected by means of screening, wherein the specific process of screening comprises: screening the crushed materials obtained by crushing through a special screen with the aperture of 10mm, taking undersize materials, screening the undersize materials obtained by the screening through a special screen with the aperture of 0.5mm, and collecting the undersize materials to obtain crushed materials with the particle size of 0.5-10 mm.
In the method of the present invention, the conditions of the first stage calcination include: the temperature is 200-250deg.C, and the time is 5-10min. Specifically, the temperature of the first stage calcination may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, or 250 ℃; the first stage calcination time may be 5min, 6min, 7min, 8min, 9min or 10min.
In the method, resin components in the waste wind power blades are primarily removed through calcination in the first stage, the temperature and time of the calcination in the first stage are controlled, and adhesion or breakage of glass fiber bundles caused by overhigh calcination temperature and overlong calcination time are avoided.
In the method of the invention, the calcination product of the first stage is soaked in acid solution, so that the adhesion between glass fiber bundles can be avoided, and the final recovery of a single glass fiber bundle product is facilitated.
In a specific embodiment, the acidic solution is selected from acetic acid solution and/or hydrochloric acid solution, preferably acetic acid solution.
In a specific embodiment, the concentration of solute in the acidic solution is 0.3-3mol/L, preferably 1.5-2.5mol/L. Specifically, the concentration of the solute in the acidic solution may be 1mol/L, 2mol/L or 3mol/L.
In a preferred embodiment, in order to avoid severe bonding between the finally recovered glass fiber bundles, in step (2), the soaking conditions include: the temperature is 80-110 ℃ and the time is 20-60min. Specifically, the soaking temperature may be controlled to 80 ℃, 90 ℃, 100 ℃ or 110 ℃, and the soaking time may be 20min, 30min, 50min or 60min.
In a preferred embodiment, in step (2), the liquid to solid ratio at the time of soaking is 10-20 mL/1 g. Further preferably 12-18 mL/1 g. Specifically, the liquid to solid ratio at the time of soaking may be 10mL:1g, 12mL:1g, 14mL:1g, 15mL:1g, 16mL:1g, 18mL:1g, 19mL:1g, or 20mL:1g.
In a specific embodiment, in the step (2), the calcined product obtained after the end of the calcination in the first stage is soaked in an acidic solution, the filtering is performed after the end of the soaking, and the filter residue obtained by the filtering is washed with water for 3-5 times and then dried in vacuum until the weight is constant, so that the material S is obtained.
In the method according to the invention, the calcination additive is selected from carbon powder and/or coal dust, preferably coal dust. According to the invention, the filter residue obtained in the step (2) and the roasting additive are mixed and calcined, so that the resin in the waste wind power blade can be removed as much as possible on the premise of ensuring the form of the glass fiber.
In a specific embodiment, the weight ratio of the calcination additive to the amount of the material S is 1:5-30, preferably 1:8-25, and more preferably 1:9-20. Specifically, the weight ratio of the calcination additive to the amount of the material S may be 1:9, 1:12, 1:14, 1:16, 1:18, 1:19, 1:20, or 1:25.
In the method of the present invention, the conditions for the second stage calcination include: the temperature is 300-450deg.C, preferably 350-430 deg.C, and the time is 10-30min. Specifically, the temperature of the second stage calcination may be 300 ℃, 320 ℃, 350 ℃, 400 ℃, 420 ℃, or 450 ℃; the second stage calcination time may be 10 minutes, 20 minutes, or 30 minutes.
In a preferred embodiment, the conditions of the second stage calcination include: the temperature is 350-430 deg.C, and the time is 10-30min.
In the method, most of resin in the waste wind power blade can be further removed through the second-stage calcination, and the strength performance of the glass fiber can be better maintained.
In a specific embodiment, in step (3), the specific process of screening the calcined product comprises: sieving the calcined product obtained in the second stage by a special screen with the aperture of 20mm, taking undersize, sieving the undersize by a screen with 40 meshes, and collecting oversize to obtain crushed aggregates with the particle size of 0.425-20 mm.
In the method of the present invention, the conditions for the third stage calcination include: the temperature is 250-450deg.C, preferably 300-400deg.C, and the time is 5-8min. Specifically, the temperature of the third stage calcination may be 250 ℃, 300 ℃, 350 ℃, 400 ℃, or 450 ℃; the temperature of the third stage calcination may be 5min, 6min, 7min or 8min.
In a preferred embodiment, the conditions of the third stage calcination include: the temperature is 300-400 ℃ and the time is 5-8min.
In the method of the invention, the third-stage calcination can further remove the resin remained in the waste wind power blade.
In a specific embodiment, the materials are calcined in a flat manner during the calcination process of the first stage calcination, the second stage calcination and the third stage calcination, so that the glass fiber bundles are further prevented from being bonded during the calcination. Specifically, in the first-stage calcination, the crushed aggregates obtained in the step (1) are tiled and then calcined; in the second stage of calcination, uniformly mixing the filter residue obtained in the step (2) with a calcination additive, and then tiling for calcination; in the third stage of calcination, the crushed aggregates obtained in the step (3) are tiled and then calcined.
In a specific embodiment, the step (4) further comprises washing the calcined product obtained after the third stage of calcination with clear water or ethanol, and then drying in vacuum to constant weight to obtain the glass fiber product.
In the method, resin in the waste wind power blades is gradually removed by three-stage calcination of the crushed waste wind power blades, excessive adhesion and crushing of glass fibers in the calcination process are avoided, the calcination temperature is reduced, the calcination time is shortened by further controlling the three-stage calcination conditions, the recovery rate of the glass fibers and the purity of the recovered glass fibers are further improved, and the method can maintain the integrity of the glass fiber form in the recovery process without losing the strength of the recovered glass fibers.
The glass fiber product obtained by the method has the microscopic morphology of a bundle-shaped structure, is single and dispersed, the internal glass fiber bundles are seldom adhered, the form of glass fibers in the original waste wind power blade is well maintained, the strength performance loss of the recycled glass fiber product is extremely low, the strength of the recycled glass fiber product is basically equal to that of the glass fibers in the original waste wind power blade, and the commercial value of the glass fiber product is higher. The glass fiber product recovered by the method can be also applied to the preparation of wind power blades or other materials needing reinforcement again, and has wider application range.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The waste wind power blades in the following examples are from the Longyuan Liaoning wind power plant.
The contents of glass fibers and resins in the discarded wind power blades in examples 1 to 4 below are shown in Table 1.
TABLE 1
Example 1
(1) Cutting waste wind power blades to obtain 210 cuboids (length is 1-20cm, width is 1-4cm, height is 2-20 cm), crushing all the cuboids, and collecting crushed aggregates with particle size of 0.5-10 mm;
(2) Tiling the crushed aggregates obtained in the step (1), calcining in a first stage at 220 ℃ for 6min, soaking the obtained calcined product in acetic acid solution (with the concentration of 2 mol/L) for 30min at 90 ℃ after the calcining in the first stage, filtering after the soaking, washing the filtered residues with water for 3-5 times, and then drying in vacuum at 80 ℃ until the weight is constant to obtain a material S;
(3) Uniformly mixing a material S and a roasting additive (carbon powder with the particle size less than or equal to 800 meshes), then carrying out second-stage roasting (the weight ratio of the material S to the roasting additive is 24:1), wherein the roasting temperature is 420 ℃, the roasting time is 10min, sieving the obtained roasted product through a special sieve with the pore size of 4mm after the second-stage roasting is finished, taking undersize, sieving the obtained undersize through a sieve with the pore size of 40 meshes (0.425 mm), and collecting oversize to obtain crushed aggregates with the particle size of 0.425-4 mm;
(4) And (3) calcining the crushed aggregates obtained in the step (3) in a third stage at the temperature of 350 ℃ for 6min, washing the obtained calcined product with ethanol for 3-5 times after the third stage is completed, and then drying the calcined product in vacuum at 80 ℃ to constant weight to obtain the glass fiber product.
Example 2
(1) Cutting the waste wind power blades to obtain 232 cuboids (length is 1-20cm, width is 1-4cm, and height is 2-20 cm), crushing all the cuboids, and collecting crushed aggregates with particle size of 0.5-6 mm;
(2) Tiling the crushed aggregates obtained in the step (1), calcining in a first stage at 230 ℃ for 6min, soaking the obtained calcined product in acetic acid solution (with the concentration of 2.5 mol/L) at 80 ℃ for 40min after the calcining in the first stage, filtering after the soaking, washing the filtered residues with water for 3-5 times, and then drying in vacuum at 80 ℃ until the weight is constant to obtain a material S;
(3) Uniformly mixing a material S and a roasting additive (pulverized coal with the particle size less than or equal to 800 meshes), spreading the mixture, carrying out second-stage roasting (the weight ratio of the material S to the roasting additive is 16:1), wherein the roasting temperature is 410 ℃, the roasting time is 12min, carrying out vibration screening on an obtained roasting product after the second-stage roasting is finished, screening the roasting product through a special screen with the pore size of 4mm, taking undersize, screening the obtained undersize through a screen with the pore size of 40 meshes (0.425 mm), and collecting oversize to obtain crushed aggregates with the particle size of 0.425-4 mm;
(4) Tiling the crushed aggregates obtained in the step (3) for third-stage calcination, wherein the calcination temperature is 380 ℃, the calcination time is 5min, washing the obtained calcination product with ethanol for 3-5 times after the third-stage calcination is finished, and then drying the obtained product in vacuum at 80 ℃ to constant weight to obtain the glass fiber product.
Example 3
(1) Cutting the waste wind power blades to obtain 220 cuboids (length is 1-20cm, width is 1-4cm, height is 2-20 cm), crushing all the cuboids, and collecting crushed aggregates with particle size of 0.5-6 mm;
(2) Tiling the crushed aggregates obtained in the step (1), calcining in a first stage at 210 ℃ for 8min, soaking the obtained calcined product in acetic acid solution (with the concentration of 1.8 mol/L) at 100 ℃ for 30min after the calcining in the first stage, filtering after the soaking, washing the filtered residues with water for 3-5 times, and then drying in vacuum at 80 ℃ until the weight is constant to obtain a material S;
(3) Uniformly mixing a material S and a roasting additive (pulverized coal with the particle size less than or equal to 800 meshes), spreading the mixture, carrying out second-stage roasting (the weight ratio of the material S to the roasting additive is 9.16:1), wherein the roasting temperature is 350 ℃, the roasting time is 20min, sieving the obtained roasting product through a sieve with the pore diameter of 4mm after the second-stage roasting is finished, taking undersize, sieving the obtained undersize through a sieve with the pore diameter of 40 meshes (0.425 mm), and collecting oversize to obtain crushed aggregates with the particle size of 0.425-4 mm;
(4) Tiling the crushed aggregates obtained in the step (3) for third-stage calcination, wherein the calcination temperature is 390 ℃, the calcination time is 6min, washing the obtained calcination product with ethanol for 3-5 times after the third-stage calcination is finished, and then drying the obtained product in vacuum at 80 ℃ to constant weight to obtain the glass fiber product.
Example 4
(1) Cutting waste wind power blades to obtain 208 cuboids (length is 1-20cm, width is 1-4cm, height is 2-20 cm), crushing all the cuboids, and collecting crushed aggregates with particle size of 0.5-10 mm;
(2) Tiling the crushed aggregates obtained in the step (1), calcining in a first stage at 240 ℃ for 6min, soaking the obtained calcined product in acetic acid solution (with the concentration of 1.5 mol/L) at 90 ℃ for 30min after the calcining in the first stage, filtering after the soaking, washing the filtered residues with water for 3-5 times, and then drying in vacuum at 80 ℃ until the weight is constant to obtain a material S;
(3) Uniformly mixing a material S and a roasting additive (carbon powder with the particle size less than or equal to 800 meshes), then carrying out second-stage roasting (the weight ratio of the material S to the roasting additive is 9.5:1), wherein the roasting temperature is 400 ℃, the roasting time is 12min, sieving the obtained roasted product through a sieve with the pore diameter of 4mm after the second-stage roasting is finished, taking undersize, sieving the obtained undersize through a sieve with the pore diameter of 40 meshes (0.425 mm), and collecting oversize to obtain crushed aggregates with the particle size of 0.425-4 mm;
(4) And (3) calcining the crushed aggregates obtained in the step (3) in a third stage at 400 ℃ for 6min, washing the obtained calcined product with ethanol for 3-5 times after the third stage is completed, and then drying the calcined product in vacuum at 80 ℃ to constant weight to obtain the glass fiber product.
Example 5
The procedure of example 2 was followed, except that the temperature of the first stage calcination was 100℃and the time of the first stage calcination was 20 minutes.
Example 6
The procedure of example 2 was followed, except that the temperature of the second stage calcination was 250℃and the time of the second stage calcination was 10 minutes.
Example 7
The procedure of example 2 was followed, except that the temperature of the third stage calcination was 500℃and the time of the third stage calcination was 6 minutes.
Example 8
The procedure of example 2 was followed, except that the rectangular parallelepiped obtained by cutting was 0.5 to 0.8mm long, 0.5 to 0.8mm wide and 0.5 to 1.5mm high.
Comparative example 1
The procedure of example 2 was followed, except that in step (1), the waste wind power blades were directly crushed and crushed into particles having a particle size of 0.5 to 6mm were collected.
Comparative example 2
The procedure of example 2 was followed, except that the first stage calcination and the third stage calcination were not performed. The specific process is as follows: soaking the crushed aggregates obtained in the step (1) in acetic acid solution at 90 ℃ for 30min, wherein the liquid-solid ratio is 10 mL/1 g when soaking, filtering after soaking, washing the filter residues obtained by filtering for 3-5 times, and then carrying out vacuum drying at 80 ℃ until the weight is constant to obtain a material S; and uniformly mixing the material S and a roasting additive (pulverized coal with the particle size less than or equal to 800 meshes), then spreading and carrying out second-stage roasting (the weight ratio of the material S to the roasting additive is 46:1), wherein the roasting temperature is 420 ℃, the roasting time is 12min, vibrating and screening the obtained roasting product after the second-stage roasting is finished, screening the roasting product through a special screen with the pore size of 4mm, taking undersize, screening the obtained undersize through a screen with the pore size of 40 meshes, and collecting oversize to obtain crushed aggregates with the particle size of 0.425-4mm so as to obtain a recovered glass fiber product.
Comparative example 3
The procedure of example 2 was followed, except that in step (2), the calcined product was directly subjected to the second stage calcination after the end of the first stage calcination, and in step (3), the amount of material S was the same as the amount of the first stage calcined product.
Test case
Test example 1
The macroscopic morphology of the glass fiber strand product recovered in example 2 was observed and the result is shown in fig. 1.
As can be seen from FIG. 1, the macroscopic morphology of the glass fibers recovered by the method of the invention is in an obvious bundle structure, and the single glass fibers are rarely bonded, which indicates that the method of the invention maintains the morphology of the original glass fibers better, and the glass fiber bundle product is recovered.
Test example 2
The strength loss rate of the glass fibers recovered in the examples and comparative examples was tested.
The testing method comprises the following steps: the glass fibers recovered in examples 1 to 8 and comparative examples 1 to 3 and the strength of the glass fiber raw material for preparing wind power blades were tested according to the method of ASTM C1557-2003 Standard test method for tensile Strength and Young's modulus of fiber, and the length of the glass fiber to be tested was ensured to be identical to the length of the glass fiber raw material during the test, according to the formula: (tensile Strength of glass fiber raw Material-tensile Strength of recovered glass fiber)/(tensile Strength of glass fiber raw Material. Times.100%, and the tensile strength loss ratio of recovered glass fiber was calculated, and the results are shown in Table 2.
Test example 3
The purity of glass fiber in the glass fiber products recovered in examples and comparative examples was tested, and the yield of glass fiber was measured.
Glass fiber purity: weighing a sample m to be measured 1 g, roasting the sample to be tested at 600 ℃ for 3 hours, collecting the product, and weighing and marking as m 2 g, according to the formula: m is m 2 /m 1 X 100%, and the content of glass fibers in the recovered glass fiber product is calculated, and the results are shown in table 2;
yield of glass fiber: the crushed aggregates obtained in the step (1) in the examples and the comparative examples have a weight of M g and the content of glass fibers in the crushed aggregates is W; examples 1-8 and comparative examples 1-3 recovered glass fiber products having a weight M b g, and testing the glass fiber in the recovered glass fiber productThe dimensional purity is W b The calculation formula of the glass fiber yield is as follows: (M) b ×W b ) The result of/(M.times.W). Times.100% is shown in Table 2.
TABLE 2
As can be seen from the results in Table 2, the method provided by the invention can reasonably recycle the waste wind power blade, and recover the glass fiber product with high purity, and the yield of the glass fiber in the waste wind power blade is higher. In addition, the glass fiber recovered by the method disclosed by the invention is in a bundle-shaped structure, and has longer length and wider application prospect.
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 (9)
1. The method for recycling the waste wind power blades is characterized by comprising the following steps of:
(1) Cutting waste wind power blades into blocks, crushing the blocks, and collecting crushed aggregates with the particle size of 0.5-10 mm;
(2) Calcining the crushed aggregates obtained in the step (1) in the first stage, soaking a calcined product in an acid solution, filtering, and washing and drying filter residues to obtain a material S;
(3) Mixing the material S with a roasting additive, then carrying out second-stage calcination, screening the calcined product, and collecting crushed aggregates with the particle size of 0.425-20 mm;
(4) Calcining the crushed aggregates obtained in the step (3) in a third stage;
the conditions of the first stage calcination include: the temperature is 200-250deg.C, and the time is 5-10min;
the conditions of the second stage calcination include: the temperature is 300-450 ℃ and the time is 10-30min;
the conditions for the third stage calcination include: the temperature is 250-450 ℃ and the time is 5-8min.
2. The method for recycling waste wind power blades according to claim 1, wherein the block is a cuboid, and the cuboid has a width of 1-4cm, a length of 1-20cm and a height of 2-20cm.
3. The method for recycling waste wind power blades according to claim 1, wherein the acidic solution is selected from acetic acid solution and/or hydrochloric acid solution.
4. The method for recycling waste wind power blades according to claim 1, wherein the concentration of solute in the acidic solution is 0.3-3mol/L.
5. The method for recycling waste wind power blades according to claim 1, wherein in the step (2), the soaking conditions include: the temperature is 80-110 ℃ and the time is 20-60min.
6. The method for recycling waste wind power blades according to claim 1, wherein in the step (2), the liquid-solid ratio during soaking is 10-20 mL/1 g.
7. The method for recycling waste wind power blades according to claim 1, wherein the roasting additive is selected from carbon powder and/or coal dust.
8. The method for recycling waste wind power blades according to claim 1, wherein the weight ratio of the roasting additive to the material S is 1:5-30.
9. The method for recycling waste wind power blades according to claim 1, wherein the waste wind power blades comprise 52-76wt% of glass fibers and 24-48wt% of resin.
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