CN115026972A - Method for harmless treatment and fiber recovery of fiber reinforced composite material waste - Google Patents
Method for harmless treatment and fiber recovery of fiber reinforced composite material waste Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 71
- 238000011084 recovery Methods 0.000 title claims abstract description 50
- 239000000835 fiber Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000000571 coke Substances 0.000 claims abstract description 12
- 239000003365 glass fiber Substances 0.000 claims description 64
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 51
- 239000004917 carbon fiber Substances 0.000 claims description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 41
- 238000005336 cracking Methods 0.000 claims description 27
- 239000011208 reinforced composite material Substances 0.000 claims description 25
- 239000010786 composite waste Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 23
- 230000008929 regeneration Effects 0.000 description 19
- 238000011069 regeneration method Methods 0.000 description 19
- 239000002131 composite material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 4
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- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000011978 dissolution method Methods 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B2017/0424—Specific disintegrating techniques; devices therefor
- B29B2017/0496—Pyrolysing the materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention discloses a method for harmless treatment and fiber recovery of fiber reinforced composite waste, which comprises the following steps: s1, treating the fiber reinforced composite material waste by superheated steam to gasify and decompose the matrix resin in the fiber reinforced composite material waste; and S2, introducing heated compressed air to treat the fibers obtained after the treatment in the step S1, and removing coke deposited on the surfaces of the fibers to obtain the clean regenerated fibers without carbon deposit residues. The invention adopts high-temperature superheated steam as anaerobic protective gas, a heating heat source and a heat transfer medium to carry out anaerobic protection and heating on fiber reinforced composite material waste, thereby completely gasifying and decomposing matrix resin in the fiber reinforced composite material waste into micromolecular gas and achieving the purpose of separating the matrix resin from fibers; and the coke deposited on the surface of the fiber is removed by adopting high-temperature hot air flow, so that the clean regenerated fiber without carbon deposit residue is obtained, the strength of the recycled regenerated fiber can reach more than 90 percent of that of the original fiber, and the performance is excellent.
Description
Technical Field
The invention belongs to the technical field of material waste recovery, and particularly relates to a method for harmless treatment and fiber recovery of fiber reinforced composite material waste.
Background
In 2018, the total output of composite materials in China is 430 ten thousand tons, which is predicted to reach 556 ten thousand tons in 2023, and the amount of newly added composite material waste materials is higher and higher in recent years, which exceeds the 2 nd level in the world in Germany and Japan. There is therefore an increasing interest in the efficient disposal of composite waste, especially fibre reinforced composite waste, and the recovery of the fibre material therein.
The existing methods for harmless treatment of fiber reinforced composite waste and recovery of fiber can be divided into landfill, incineration, crushing, separation and the like. Landfill and incineration are gradually prohibited, and the pulverization method cannot sufficiently exert the excellent properties of the fiber. The most promising recovery method at home and abroad is a separation method, which decomposes a resin matrix into organic micromolecular gas by a pyrolysis or dissolution method to realize the separation of fibers and the resin matrix, thereby obtaining the recovery method of regenerated fibers. For example, three industrial carbon fiber recovery companies, namely ELG, Japan carbon fiber recovery company and MIT-RCF company in America, all adopt a high-temperature thermal cracking recovery technology, and the method is to directly burn a carbon fiber reinforced composite material or heat and vaporize the carbon fiber reinforced composite material in a nitrogen atmosphere to recover carbon fiber precursors, but the recovered regenerated fibers have serious performance damage, higher recovery cost and pollution and cannot be effectively popularized.
In the prior patent document CN106810722A, a method for recovering carbon fibers from waste carbon fiber reinforced composite materials is described, which comprises the steps of cutting carbon fiber reinforced composite materials, soaking in absolute ethyl alcohol, drying, and then performing heat treatment at 400-. However, the method needs cutting in advance, cannot directly treat products with different specifications and shapes, adopts chemical reagents, generates waste liquid, can only treat thermosetting carbon fibers, and cannot treat other products. It is obvious from the electron micrograph 2B of the optimum processing technology, namely the temperature of 450 ℃ and the time of 90min that impurities still exist.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for harmless treatment of fiber reinforced composite waste and fiber recovery.
The purpose of the invention is realized by the following technical scheme:
the invention provides a method for harmless treatment and recovery of fiber reinforced composite waste, which comprises the following steps:
s1, treating the fiber reinforced composite material waste by superheated steam to gasify and decompose the matrix resin in the fiber reinforced composite material waste;
and S2, introducing heated compressed air to treat the fibers obtained after the treatment in the step S1, and removing coke deposited on the surfaces of the fibers to obtain the clean regenerated fibers without carbon deposit residues.
Preferably, the fiber reinforced composite waste includes at least one of glass fiber reinforced composite waste and carbon fiber reinforced composite waste.
Preferably, in step S1, the superheated steam has an oxygen content of less than 0.3%.
Preferably, the superheated steam is superheated steam with the temperature of 400-700 ℃ and the normal pressure. The fiber reinforced composite material waste is treated by superheated steam with the temperature of 400-700 ℃ under normal pressure, so that the fiber reinforced composite material waste is not oxidized and burnt, only matrix resin on the surface is gasified, and fibers in the fiber are not reacted and changed, thereby realizing the separation of the fibers and the matrix resin.
As a further preferable scheme, when the fiber reinforced composite material waste is carbon fiber reinforced composite material waste, the normal pressure temperature of the superheated steam is 30-50 ℃ higher than the cracking temperature of matrix resin in the carbon fiber reinforced composite material waste; if the temperature of the adopted superheated steam is too low, the cracking rate of the matrix resin is reduced, and the cracking time is too long; when the temperature of the superheated steam is too high, the carbon fiber is damaged to a certain extent. For example, when the cracking temperature of the matrix resin in the carbon fiber composite reinforced material waste to be treated is 450 ℃, the optimum treatment effect can be achieved by using superheated steam with the normal pressure of 480-500 ℃.
When the fiber reinforced composite waste is the glass fiber reinforced composite waste, the temperature of the superheated steam at normal pressure is 0-30 ℃ higher than the cracking temperature of matrix resin in the glass fiber reinforced composite waste. If the temperature of the adopted superheated steam is too low, the cracking rate of the matrix resin is reduced, and the cracking time is too long; when the temperature of the superheated steam is too high, the glass fiber is damaged to a certain extent, and the performance of the regenerated glass fiber is obviously damaged due to the brittleness of the glass fiber compared with that of the carbon fiber. For example, when the cracking temperature of the matrix resin in the waste of the glass fiber composite reinforced material to be treated is 450 ℃, the temperature of the normal pressure of the superheated steam adopted is 450-480 ℃, so that the best treatment effect can be achieved.
Preferably, in step S1, the superheated steam treatment is performed for 1 to 6 hours.
As a further preferable mode, the time of the superheated steam treatment is 1 to 3 hours.
Preferably, in step S1, the combustible small molecule gas generated by the gasification and decomposition of the matrix resin is discharged together with the superheated steam and then introduced into a thermal energy conversion system, and after combustion, the gas becomes a heat source at about 900 ℃.
Preferably, in step S2, the temperature of the heated compressed air is 400-500 ℃.
Preferably, the strength of the regenerated fiber is 90% or more of the fibril strength.
More preferably, the strength of the regenerated fiber is 98% or more of the fibril strength.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention adopts high-temperature superheated steam as anaerobic protective gas, a heating heat source and a heat transfer medium to carry out anaerobic protection and heating on the fiber reinforced composite material waste, thereby completely gasifying and decomposing matrix resin in the fiber reinforced composite material waste into micromolecular gas (the cracking rate is as high as 99 percent) and achieving the purpose of separating the matrix resin from fibers; and the coke deposited on the surface of the fiber is removed by adopting high-temperature hot air flow, so that the regenerated fiber which is clean and free of carbon deposit residue and has the recovery rate of 99% is obtained, the strength of the regenerated fiber obtained by recovery can reach more than 90% of that of the original fiber, and the performance is excellent.
2) The method of the invention does not need to carry out any pretreatment on the fiber reinforced composite material waste, but directly carries out high-temperature superheated steam treatment, thereby greatly simplifying the recovery process.
3) The method overcomes the technical difficulty of realizing zero-pollution recovery of the fiber reinforced composite material waste, has high recovery efficiency, basically has no damage to the recovered regenerated fiber and low recovery cost, and lays a solid foundation for harmless treatment of the fiber reinforced composite material waste and industrialization and market application of fiber recovery.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a drawing of regenerated glass fibers recovered from the processing of waste fan blade composite material in accordance with an embodiment of the present invention; wherein, FIG. 1A is a composite material of a waste fan blade; FIG. 1B is a regenerated glass fiber;
FIG. 2 is an electron micrograph of recycled carbon fibers recycled from carbon fiber reinforced composite waste treatment according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides a method for harmless treatment of glass fiber reinforced composite waste and recovery of glass fibers, which comprises the following steps:
1) putting the glass fiber reinforced composite waste (in the embodiment, the waste fan blade composite material, as shown in fig. 1A) into a regeneration treatment furnace, closing the furnace door, introducing superheated steam with the normal pressure and the temperature of 450 ℃ to expose the glass fiber reinforced composite waste to the superheated steam, and treating at 450 ℃ for 3 hours to crack and gasify the matrix resin (the cracking temperature of which is 450 ℃) in the glass fiber reinforced composite waste into micromolecular gas (the resin cracking rate is 99%). Combustible gas in the obtained small molecular gas and superheated steam are discharged together and then can enter a heat energy conversion system for recycling, so that a heat source is provided.
2) And (2) after the treatment of the step 1), stopping introducing the superheated steam into the regeneration treatment furnace, and introducing heated compressed air (at the temperature of 500 ℃) to completely remove coke deposited on the surfaces of the glass fibers left after the matrix resin is gasified.
3) And 2) after the treatment in the step 2), stopping introducing the compressed air, opening a furnace door of the regeneration treatment furnace, and taking out the regenerated glass fiber, wherein the obtained regenerated glass fiber is clean, free of carbon deposit residue and free of damage as shown in figure 1B. The recovery rate of the regenerated glass fiber reaches 99 percent.
Example 2
The embodiment provides a method for harmless treatment of glass fiber reinforced composite waste and recovery of glass fibers, which comprises the following steps:
1) putting the glass fiber reinforced composite material waste (in the embodiment, the waste fan blade composite material) into a regeneration treatment furnace, closing a furnace door, introducing superheated steam with the normal pressure and the temperature of 460 ℃, exposing the glass fiber reinforced composite material waste to the superheated steam, and treating at 460 ℃ for 2 hours to crack and gasify the matrix resin (the cracking temperature of which is 450 ℃) in the glass fiber reinforced composite material waste into micromolecular gas (the cracking rate of the resin is 99%). Combustible gas in the obtained small molecular gas and superheated steam are discharged together and then can enter a heat energy conversion system for recycling, so that a heat source is provided.
2) And (2) after the treatment of the step 1), stopping introducing the superheated steam into the regeneration treatment furnace, and introducing heated compressed air (the temperature is 400 ℃) to completely remove coke deposited on the surfaces of the glass fibers left after the matrix resin is gasified.
3) And 2) after the treatment of the step 2), stopping introducing the compressed air, opening a furnace door of the regeneration treatment furnace, and taking out the regenerated glass fibers to be clean without carbon deposit residue and damage. The recovery rate of the regenerated glass fiber reaches 99 percent.
Example 3
The embodiment provides a method for harmless treatment of glass fiber reinforced composite waste and recovery of glass fibers, which comprises the following steps:
1) putting the glass fiber reinforced composite material waste (in the embodiment, the waste fan blade composite material) into a regeneration treatment furnace, closing a furnace door, introducing superheated steam with normal pressure and the temperature of 480 ℃, exposing the glass fiber reinforced composite material waste to the superheated steam, and treating at 480 ℃ for 1 hour to crack and gasify the matrix resin (the cracking temperature of which is 450 ℃) in the glass fiber reinforced composite material waste into micromolecular gas (the cracking rate of the resin is 99%). Combustible gas in the obtained small molecular gas and superheated steam are discharged together and then can enter a heat energy conversion system for recycling, so that a heat source is provided.
2) After the treatment of the step 1), stopping introducing the superheated steam into the regeneration treatment furnace, and introducing heated compressed air (the temperature is 450 ℃) to completely remove coke deposited on the surfaces of the glass fibers remained after the gasification of the matrix resin.
3) And 2) after the treatment of the step 2), stopping introducing the compressed air, opening a furnace door of the regeneration treatment furnace, and taking out the regenerated glass fibers to be clean without carbon deposit residue and damage. The recovery rate of the regenerated glass fiber reaches 99 percent.
Example 4
This example provides a method for harmless treatment of waste glass fiber reinforced composite material and recovery of glass fiber, which is substantially the same as the steps of example 1, except that: in the step 1), superheated steam with the temperature of 420 ℃ under normal pressure is adopted for treatment for 6 hours. The cracking rate of the matrix resin is 95%, a little resin residue, no carbon deposit residue and no damage exist on the surface of the finally obtained regenerated glass fiber, and the recovery rate of the regenerated glass fiber is 97%.
Example 5
This example provides a method for harmless treatment of waste glass fiber reinforced composite material and recovery of glass fiber, which is substantially the same as the steps of example 1, except that: in the step 1), superheated steam with the temperature of 500 ℃ at normal pressure is adopted for treatment for 1 hour. The cracking rate of the matrix resin is 99 percent, the finally obtained regenerated glass fiber is clean and has no carbon residue, but the surface of the fiber is damaged to a certain extent, and the recovery rate of the regenerated glass fiber is 96 percent.
Example 6
The embodiment provides a method for harmless treatment and carbon fiber recovery of carbon fiber reinforced Composite (CFRP) waste, which comprises the following steps:
1) putting the carbon fiber reinforced composite material waste into a regeneration treatment furnace, closing a furnace door, introducing superheated steam with the normal pressure and the temperature of 500 ℃ to expose the carbon fiber reinforced composite material waste to the superheated steam, and treating at the temperature of 500 ℃ for 1 hour to crack and gasify matrix resin (the cracking temperature is 450 ℃) in the waste into micromolecular gas (the cracking rate of the resin is 99%). Combustible gas in the obtained small molecular gas and superheated steam are discharged together and then can enter a heat energy conversion system for recycling, so that a heat source is provided.
2) And (2) after the treatment of the step 1), stopping introducing superheated steam into the regeneration treatment furnace, and introducing heated compressed air (at the temperature of 400 ℃) to completely remove coke deposited on the surface of the carbon fiber left after the matrix resin is gasified.
3) And 2) after the treatment in the step 2), stopping introducing the compressed air, opening a furnace door of the regeneration treatment furnace, taking out the regenerated carbon fibers, wherein the regenerated carbon fibers are clean, free of carbon deposit residues and free of damage, and an electron microscope photo of the regenerated carbon fibers is shown in fig. 2. The recovery rate of the regenerated carbon fiber reaches 99 percent.
Example 7
The embodiment provides a method for harmless treatment of carbon fiber reinforced Composite (CFRP) waste and recovery of carbon fibers, which comprises the following steps:
1) putting the carbon fiber reinforced composite material waste into a regeneration treatment furnace, closing a furnace door, introducing superheated steam with the normal pressure and the temperature of 450 ℃ to expose the carbon fiber reinforced composite material waste to the superheated steam, and treating at 450 ℃ for 3 hours to crack and gasify matrix resin (the cracking temperature is 450 ℃) in the carbon fiber reinforced composite material waste into micromolecular gas (the cracking rate of the resin is 95%). Combustible gas in the obtained small molecular gas and superheated steam are discharged together and then can enter a heat energy conversion system for recycling, so that a heat source is provided.
2) And (2) after the treatment of the step 1), stopping introducing superheated steam into the regeneration treatment furnace, and introducing heated compressed air (at the temperature of 500 ℃) to completely remove coke deposited on the surface of the carbon fiber left after the matrix resin is gasified.
3) And 2) after the treatment in the step 2), stopping introducing the compressed air, opening a furnace door of the regeneration treatment furnace, and taking out the regenerated carbon fibers, wherein the surface of the regenerated carbon fibers has a little resin residue, no carbon deposit residue and almost no damage. The recovery rate of the regenerated carbon fiber reaches 95 percent.
Example 8
The embodiment provides a method for harmless treatment and carbon fiber recovery of carbon fiber reinforced Composite (CFRP) waste, which comprises the following steps:
1) putting the carbon fiber reinforced composite material waste into a regeneration treatment furnace, closing a furnace door, introducing superheated steam with normal pressure and the temperature of 480 ℃ to expose the carbon fiber reinforced composite material waste into the superheated steam, and treating at 480 ℃ for 1.5 hours to crack and gasify matrix resin (the cracking temperature is 450 ℃) in the waste into micromolecular gas (the resin cracking rate is 99%). Combustible gas in the obtained small molecular gas and superheated steam are discharged together and then can enter a heat energy conversion system for recycling, so that a heat source is provided.
2) And (2) after the treatment in the step 1), stopping introducing superheated steam into the regeneration treatment furnace, and introducing heated compressed air (the temperature is 450 ℃) to completely remove coke deposited on the surface of the carbon fiber left after the matrix resin is gasified.
3) And 2) after the treatment in the step 2), stopping introducing the compressed air, opening a furnace door of the regeneration treatment furnace, and taking out the regenerated carbon fibers to be clean without carbon deposit residue and damage. The recovery rate of the regenerated carbon fiber reaches 99 percent.
Example 9
This example provides a method for harmless treatment of carbon fiber reinforced composite waste and recovery of carbon fiber, which is substantially the same as the steps in example 6, except that: in step 1), superheated steam at 520 ℃ under normal pressure is used for treatment for 1 hour. The cracking rate of the matrix resin is 99%, the finally obtained regenerated carbon fiber is clean and has no carbon deposit residue, but the surface of the fiber is damaged to a certain extent, and the recovery rate of the regenerated carbon fiber is 97%.
Comparative example 1
This comparative example provides a method for the harmless treatment of glass fiber reinforced composite waste and the recovery of glass fibers, which is substantially the same as example 1 except that: in step 2), the temperature of the introduced compressed air was 550 ℃.
This temperature is too high, resulting in significant damage to the surface of the resulting regenerated glass fibers.
Comparative example 2
The comparative example provides a method for harmless treatment of glass fiber reinforced composite waste and recovery of glass fiber, which is substantially the same as that of example 2, except that: in step 2), the temperature of the introduced compressed air is 350 ℃.
At the temperature, coke deposited on the surface of the glass fiber left after the gasification of the matrix resin cannot be completely removed, and more carbon residues are deposited on the surface of the obtained regenerated glass fiber.
Comparative example 3
The comparative example provides a method for harmless treatment of glass fiber reinforced composite waste and recovery of glass fiber, which is substantially the same as in example 1 except that: in the step 1), the adopted superheated steam is superheated steam with normal pressure and 350 ℃ for 6 hours.
The cracking rate of the resin under the treatment is 88%, and more resin is not cracked and gasified, so that the surface of the prepared regenerated glass fiber is not clean.
Performance testing
Tensile strength, modulus and elongation of the diameter glass fibers recovered after the treatment in example 1 were measured and measured by INSTRON-5966, the results of which are shown in Table 1. From the data in Table 1, it is understood that the average tensile strength of glass fibers having an average diameter of 16.02 μm after recovery is 1356MPa, and that the tensile strength of the glass fibers after recovery is almost equivalent to the strand strength, as compared with the average tensile strength of glass fibers having an average diameter of about 15 μm reported in the literature, which is about 1300 MPa. Therefore, the recycled regenerated glass fiber performance of the glass fiber reinforced composite material is not obviously reduced.
TABLE 1
The tensile strength, modulus and elongation of the glass fibers of different diameters recovered after the treatment in the methods of examples 2 to 5 were measured by INSTRON-5966, and the results are shown in Table 2 (the measurement results are the average values of a plurality of samples). The results in Table 2 show that the tensile strength of the recovered glass fibers having a diameter of 15 μm was 90% or more of the tensile strength of the glass fibers described in the literature. Comparing the results of example 1 and example 5, it can be seen that the tensile strength, modulus and elongation after recovery of the glass fiber are significantly inferior to those of example 1 due to the excessively high temperature of the superheated steam used in example 5.
TABLE 2
The tensile strength of the recycled carbon fiber monofilaments treated by the methods of examples 6 to 9 was measured, and the tensile strength of the carbon fiber monofilaments before treatment was compared, and the results are shown in table 3 (the results are all the average values of a plurality of samples). As can be seen from the comparison of the data in Table 3, the average strength of the monofilaments after the regeneration of the carbon fiber reinforced composite material reaches more than 98 percent of the strength of the precursor, and the performance of the monofilaments is not influenced.
TABLE 3
The invention has many applications and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the spirit of the invention, and these modifications should be construed as within the scope of the invention.
Claims (10)
1. A method for harmless treatment and fiber recovery of fiber reinforced composite waste is characterized by comprising the following steps:
s1, treating the fiber reinforced composite material waste by superheated steam to gasify and decompose the matrix resin in the fiber reinforced composite material waste;
and S2, introducing heated compressed air to treat the fibers obtained after the treatment in the step S1, and removing coke deposited on the surfaces of the fibers to obtain the clean regenerated fibers without carbon deposit residues.
2. The method of claim 1, wherein the fiber-reinforced composite waste comprises at least one of glass fiber-reinforced composite waste and carbon fiber-reinforced composite waste.
3. The method of claim 1, wherein the superheated steam has an oxygen content of less than 0.3% in step S1.
4. The method for harmless treatment and fiber recovery of fiber reinforced composite waste as claimed in claim 1 or 2, wherein the superheated steam is a superheated steam with a temperature of 400-700 ℃ at normal pressure.
5. The method for harmless treatment and fiber recovery of fiber reinforced composite waste according to claim 4, wherein when the fiber reinforced composite waste is carbon fiber reinforced composite waste, the atmospheric temperature of the superheated steam is 30-50 ℃ higher than the cracking temperature of the matrix resin in the carbon fiber reinforced composite waste;
when the fiber reinforced composite material waste is the glass fiber reinforced composite material waste, the normal pressure temperature of the superheated steam is 0-30 ℃ higher than the cracking temperature of the matrix resin in the glass fiber reinforced composite material waste.
6. The method for detoxifying and recovering fiber according to claim 1, wherein the time of the superheated steam treatment in step S1 is 1-6 hours.
7. The method for harmless treatment and fiber recovery of fiber reinforced composite waste according to claim 6, wherein the time of the superheated steam treatment is 1-3 hours.
8. The method as claimed in claim 1, wherein the temperature of the heated compressed air in step S2 is 400-500 ℃.
9. The method for detoxifying fiber-reinforced composite material waste and recovering fiber according to claim 1, wherein the strength of the regenerated fiber is 90% or more of the fibril strength.
10. The method for detoxifying and recovering fiber from fiber-reinforced composite waste according to claim 1, wherein the strength of the regenerated fiber obtained is 98% or more of the fibril strength.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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