CN107032346B - The method for recycling carbon fiber enhancement resin base composite material - Google Patents
The method for recycling carbon fiber enhancement resin base composite material Download PDFInfo
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- CN107032346B CN107032346B CN201710364919.2A CN201710364919A CN107032346B CN 107032346 B CN107032346 B CN 107032346B CN 201710364919 A CN201710364919 A CN 201710364919A CN 107032346 B CN107032346 B CN 107032346B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
- B01J3/062—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies characterised by the composition of the materials to be processed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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Abstract
This disclosure relates to a kind of method for recycling carbon fiber enhancement resin base composite material, method includes the following steps: a, carbon fiber enhancement resin base composite material crushed be for partial size 10-500 mesh micro mist；B, it is pressed and molded after mixing the micro mist obtained in step a with porous nano alloy addition, obtains molding micro mist, it is 0.01-10 μm of micropore that the porous nano alloy addition, which has diameter,；C, the molding micro mist obtained in step c is subjected to phase transformation processing, generates diamond.Discarded carbon fiber enhancement resin base composite material recycling can be changed into the diamond of high added value by this method.
Description
Technical field
This disclosure relates to a kind of method for recycling carbon fiber enhancement resin base composite material.
Background technique
Carbon fiber enhancement resin base composite material (Carbon Fiber Reinforced Polymer, hereinafter referred to as
CFRP) have many advantages, such as lightweight, high intensity, high ratio modulus, it is antifatigue, corrosion-resistant, can design and moulded manufacturability is good, in aviation
The fields such as space flight, sports equipment, wind electricity blade, building reinforcing, the vehicles are widely applied.CFRP mostly uses thermosetting property
Polymer is as matrix resin, it is difficult to handle.It is also more and more using more and more extensive, discarded CFRP with CFRP, it gives up
The new problem that the recycling of gurry becomes industrial circle and society faces.Containing a large amount of expensive carbon fibers in CFRP, directly will
Although it fills economy and saves money, expensive carbon fiber is wasted.In face of multiple pressure, developing low-cost, greenization waste carbon
Fibrous composite recycling and reutilization technology are very urgent.
The a large amount of carbon based substances mixture such as carbon fiber, thermoplastic resin, adhesive is usually contained in waste, at classification
Reason increases the difficulty of its recovery processing.The recovery method of discarded CFRP mainly has physiochemical mutagens, energy regenerating and chemistry at present
Recycling.Discarded CFRP is mainly broken into particle or is milled into powder and is directly used as filler or is added to pave the way by physiochemical mutagens method
In material, cement, this method processing mode is simple, cost is relatively low, but obtain it is most of be low value reconstituted product, it is right
For the CFRP containing high value carbon fiber and it is not suitable for.Energy regenerating is by burning the organic matter in CFRP waste simultaneously
Using the method for its energy, the recovery method simple process, but CFRP waste can discharge toxic gas during the burning process,
Cause secondary pollution.Chemical recycling can obtain the carbon fiber of high value, but need a large amount of solvent during processing, make
At environmental pollution.Therefore it is necessary to develop a kind of high-quality method for recycling CFRP.
Summary of the invention
Purpose of this disclosure is to provide a kind of method for recycling carbon fiber enhancement resin base composite material, this method can be incited somebody to action
Discarded carbon fiber enhancement resin base composite material recycling is changed into the diamond of high added value.
To achieve the goals above, the disclosure provides a kind of method for recycling carbon fiber enhancement resin base composite material, should
Method the following steps are included:
A, carbon fiber enhancement resin base composite material is crushed be for partial size 10-500 mesh micro mist；
B, it is pressed and molded, is formed after mixing the micro mist obtained in step a with porous nano alloy addition
Micro mist, it is 0.01-10 μm of micropore that the porous nano alloy addition, which has diameter,；
C, the molding micro mist obtained in step c is subjected to phase transformation processing, generates diamond.
Optionally, this method further include: in step a, the step of the micro mist is dried, the temperature of the drying
Are as follows: 80-150 DEG C, time 8-24h.
Optionally, in step b, the preparation step of the porous nano alloy addition includes:
(1) it handles 0.5-3 hours, obtains at 60-120 DEG C after mixing the first metal salt, the second metal salt with hydrolytic reagent
To the first mixture, the metal in first metal salt be selected from least one of iron, copper, cobalt, tin, nickel and aluminium, it is described
Metal in second metal salt is selected from least one of yttrium, lanthanum and cerium；
(2) first mixture obtained in step (1) is mixed with particle size controling agent, handles 1- at 80-150 DEG C
6 hours, obtain the second mixture；
(3) second mixture for obtaining step (2) is mixed with carrier, is handled 0.5-3 hours at 80-150 DEG C,
Then it is filtered, washed, resulting solid material is roasted 1-5 hours at 600-1000 DEG C, three-phase amorphous state micropore is obtained and receives
Meter He Jin；
(4) three-phase amorphous state porous nano alloy obtained in step (3) is mixed with elemental metals, is then existed
Handled 1-2 hours at 150-250 DEG C, obtain porous nano alloy addition, the elemental metals be selected from iron, copper, cobalt, nickel and
At least one of zinc.
Optionally, in step (1), the weight ratio of first metal salt, the second metal salt and hydrolytic reagent is 1:(0.01-
0.5): (1-30).
Optionally, in step (1), the hydrolytic reagent is selected from least one of glycerine, isopropanol and n-butanol.
Optionally, in step (2), the particle size controling agent in step (2) is rubbed with the hydrolytic reagent in step (1)
You are than being 1:(0.1-5).
Optionally, in step (2), the particle size controling agent is selected from ammonium hydroxide, sodium hydroxide, ammonium chloride, acetamide, Sanya
At least one of ethyldiamine, diethylenetriamines and isopropanolamine.
Optionally, in step (3), on the basis of first metal salt of 100 parts by weight, the dosage of the carrier is
30-200 parts by weight.
Optionally, in step (3), the carrier is selected from least one of aluminium oxide, active carbon and lamellar graphite.
Optionally, in step (4), the weight ratio of the three-phase amorphous state porous nano alloy and elemental metals is 1:(5-
100)。
Optionally, in step b, in step b, the weight ratio of the micro mist and porous nano alloy addition is 1:(0.5-
5)。
Optionally, this method further include: in step b, the micro mist is mixed with porous nano alloy addition, adhesive
After be pressed and molded, obtain molding micro mist, on the basis of the micro mist of 100 parts by weight, the dosage of the adhesive is that 0.2-5 is weighed
Part is measured, the adhesive is selected from least one of epoxy resin, phenolic resin and Lauxite.
Optionally, in step b, the pressure of the compression molding is 20-150MPa.
Optionally, the compactness of the molding micro mist obtained in step b is not less than 75%.
Optionally, the condition of the phase transformation processing in step c are as follows: oxygen content is not more than 3% in air atmosphere, and temperature is
2000-2500 DEG C, pressure 10000-100000MPa.
Optionally, the partial size of the diamond is 0.01-10 μm.
Through the above technical solutions, the method that the disclosure provides can be by discarded carbon fiber enhancement resin base composite material
It is changed into the higher diamond of added value, reduces the severe of changing condition, carbon fiber enhancement resin base composite wood
Expect that conversion ratio and diamond yield are higher.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific
Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of method for recycling carbon fiber enhancement resin base composite material, method includes the following steps:
A, carbon fiber enhancement resin base composite material is crushed be for partial size 10-500 mesh micro mist；
B, it is pressed and molded, is formed after mixing the micro mist obtained in step a with porous nano alloy addition
Micro mist, it is 0.01-10 μm of micropore that the porous nano alloy addition, which has diameter,；
C, the molding micro mist obtained in step c is subjected to phase transformation processing, generates diamond.
There is the porous nano alloy addition of special microcellular structure by adding, the method that the disclosure provides can will give up
The carbon fiber enhancement resin base composite material of abandoning is changed into the higher diamond of added value, reduces the harshness of changing condition
Degree, conversion ratio is up to 20% or more.
According to the disclosure, the particle diameter distribution of carbon fiber enhancement resin base composite material micro mist be will affect in its phase transition process
Conversion ratio, if the partial size of micro powder granule is too big (> 10 mesh), then the surface of micro powder granule can be lower, needs in conversion higher
Energy, while will cause particle partial phase change, it forms diamond phase and graphite-phase mutually adulterates staggered confusion, be unable to get knot
The uniform cubic type diamond lattic structure of structure；Particle is too small, then machining can be brought difficult.Therefore, it in step a, needs first
Discarded carbon fiber enhancement resin base composite material is cut, is crushed or milled, crushing as partial size is that 10-500 purpose is micro-
Powder.In addition, it can include the step of micro mist is dried.The condition of the drying can be this field routine,
For example, dry temperature can be with are as follows: 80-150 DEG C, the time can be 8-24 hours.
According to the disclosure, by the way that into the micro mist, there is the porous nano of special microcellular structure to close for addition in stepb
Golden additive can improve the acoustic reactance (1000-5000kg/m of molding micro mist in phase transformation treatment process2S), molding micro mist is made to exist
Temperature needed for phase transformation can be reached in short time；It can be catalyzed, accelerate in carbon fiber enhancement resin base composite material simultaneously
The differentiation of organic molecule cracks, and reduces the activation energy of carbon based substances phase transformation conversion, improves transformation efficiency.The porous nano
The micropore size of alloy addition can be measured using method well-known to those skilled in the art.
According to the disclosure, in step b, the preparation step of the porous nano alloy addition may include:
(1) it handles 0.5-3 hours, obtains at 60-120 DEG C after mixing the first metal salt, the second metal salt with hydrolytic reagent
To the first mixture, the metal in first metal salt be selected from least one of iron, copper, cobalt, tin, nickel and aluminium, it is described
Metal in second metal salt is selected from least one of yttrium, lanthanum and cerium；
(2) first mixture obtained in step (1) is mixed with particle size controling agent, handles 1- at 80-150 DEG C
6 hours, obtain the second mixture；
(3) second mixture for obtaining step (2) is mixed with carrier, handles 1-6 hours at 80-150 DEG C, so
After be filtered, washed, resulting solid material is roasted 1-5 hours at 600-1000 DEG C, obtains three-phase amorphous state porous nano
Alloy；
(4) three-phase amorphous state porous nano alloy obtained in step (3) is mixed with elemental metals, is then existed
Handled 1-2 hours at 150-250 DEG C, obtain porous nano alloy addition, the elemental metals be selected from iron, copper, cobalt, nickel and
At least one of zinc.
According to the disclosure, in step (1), first metal salt and the second metal salt refer to respectively with the first metal and
Two metals are the compound of cation, and the salt can be nitrate, sulfate or chlorate etc., preferably nitrate.Institute
State the first metal salt, the second metal salt and alcohol weight ratio be can be with 1:(0.01-0.5): (1-30).The hydrolytic reagent can make
Micro- hydrolysis occurs for first metal salt and the second metal salt in favor of forming microcellular structure, such as can be for selected from the third three
At least one of alcohol, isopropanol and n-butanol, the concentration of above-mentioned substance can be 0.05-1g/ml.
According to the disclosure, in step (2), the particle size controling agent can control resulting three-phase amorphous during the reaction
The particle size of state porous nano alloy, so that the porous nano alloy addition forms suitable partial size to further make
Diamond forms suitable partial size.The particle size controling agent can be acid or alkaloids, in order to make prepared micropore
Nanoalloy additive forms the particle of spherical shape, and the particle size controling agent is preferably alkaline matter, such as can be inorganic
Alkali and/or organic amine, the inorganic base can be described organic for selected from least one of ammonium hydroxide, sodium hydroxide and ammonium chloride
Amine can be for selected from least one of acetamide, triethylenediamine, diethylenetriamines and isopropanolamine.The partial size control
Preparation is most preferably ammonium hydroxide.The institute in the particle size controling agent and step (1) in order to reach ideal effect, in step (2)
The molar ratio for stating hydrolytic reagent is 1:(0.1-5), when the particle size controling agent contains nitrogen in terms of N, the particle size controling agent is not
With OH when Nitrogen element-Meter.
According to the disclosure, in step (3), on the basis of first metal salt of 100 parts by weight, the dosage of the carrier
It can be 30-200 parts by weight.The carrier can for example, can select for this field as the conventional selection of catalyst carrier
At least one of self-alumina, active carbon and lamellar graphite.In order to reduce the introducing of impurity, the carrier is preferably aoxidized
Aluminium.
According to the disclosure, in step (4), the weight ratios of the three-phase amorphous state porous nano alloy and elemental metals can be with
For 1:(5-100).
According to the disclosure, the porous nano alloy addition can play under suitable dosage improves phase transformation conversion ratio
Effect, in step b, the weight ratio of the micro mist and porous nano alloy addition can be 1:(0.5-5), preferably 1:
(1.5-2.5)。
According to the disclosure, in order to be more advantageous to molding, this method can also include: in step b, by the micro mist and micropore
It is pressed and molded after Nanoalloy additive, adhesive mixing, obtains molding micro mist.The dosage and type of the adhesive can be
It is well known to those skilled in the art, for example, on the basis of the micro mist of 100 parts by weight, the dosage of the adhesive can be
0.2-5 parts by weight, the adhesive can be for selected from least one of epoxy resin, phenolic resin and Lauxites.
According to the disclosure, in step b, the condition of the compression molding can be the normal condition of this field, for example, described
The pressure of compression molding can be 20-150MPa.The shape for being molded obtained molding micro mist can be spherical or cheese.In mould
During pressure, the micro mist need to be sufficiently compacted, obtained in step b it is described molding micro mist compactness be not less than 75%, compared with
High compactness can reduce the pressure needed for phase transition process and temperature, so as under the conditions of lower pressure and temperature
Carry out the phase transformation conversion of carbon.
According to the disclosure, the phase transformation in step c processing can in equipment well-known to those skilled in the art into
Row, such as can be carried out in the dedicated shock wave equipment of phase transformation, the shock wave equipment is commercially available.Pass through the aforementioned of the disclosure
Step can reduce the severe of phase transformation treatment process condition, the condition of the phase transformation processing are as follows: air atmosphere in adjustment equipment
Middle oxygen content is no more than 3%, and temperature is 2000-2500 DEG C, pressure 10000-100000MPa.Under the above conditions, it forms
Carbon fibre composite in micro mist cracks first, releases H2、N2、H2The small molecules such as O, phase occurs for carbon based substances later
Become, generates diamond.The particle diameter distribution of obtained diamond is 0.01-10 μm.
It is higher that discarded carbon fiber enhancement resin base composite material can be changed into added value by the method that the disclosure provides
Diamond, reduce the severe of changing condition, carbon fiber enhancement resin base composite material conversion ratio and artificial gold
Hard rock yield is higher, and resulting diamond has preferable performance.
The disclosure is further described below by embodiment, but is not intended to limit the present invention.
In embodiment and comparative example, according to the micropore of GB/T 19587-2004 method measurement porous nano alloy addition
Size.
In embodiment and comparative example, carbon fiber enhancement resin base composite material conversion ratio and diamond yield according to
Lower formula calculates:
Conversion ratio (%)=carbon fiber enhancement resin base composite material micro mist is converted into weight/carbon fiber of diamond
Weight × 100% of carbon in reinforced resin based composites micro mist；
The weight for the diamond that yield (%)=recycling obtains/carbon fiber enhancement resin base composite material micro mist conversion
For weight × 100% of diamond.
It is raw materials used in addition to special instruction in embodiment, it is commercially available chemically pure reagent.
Embodiment 1
(1) porous nano alloy addition is prepared
By weight be weight ratio by the first metal salt ferric nitrate, the second metal salt cerous nitrate and hydrolytic reagent glycerine it is 1:
0.05:20 mixing, is then vigorously stirred 0.5h at 80 DEG C, obtains the first mixture.Backward first mixture in grain is added
Diameter controlling agent ammonium hydroxide (concentration is 20 weight %), the molar ratio of ammonium hydroxide (in terms of N) and glycerine is 1:3, after being added dropwise, 80
Continue to stir 1h at DEG C, obtains the second mixture.Alumina catalyst support is added into the second mixture again, with the of 100 parts by weight
On the basis of one metal salt ferric nitrate, the dosage of aluminium oxide is 80 parts by weight, continues to stir 1h at 120 DEG C, then cooling, mistake
Filter, washing, disperse resulting solid material on quartz plate, roast 5 hours for 800 DEG C, are obtained with micropore in Muffle furnace
Three-phase amorphous state porous nano alloy, micro-pore diameter be 1-8 μm.Then by resulting three-phase amorphous state porous nano alloy with
Elemental metals iron uniformly mixes, and the weight ratio of the three-phase amorphous state porous nano alloy and elemental metals iron is 1:30, in 200
1h is handled at DEG C, obtains porous nano alloy addition.
(2) carbon fiber enhancement resin base composite material micro mist is prepared
Discarded carbon fiber enhancement resin base composite material is passed through cutting, is broken into molecule or is milled into 10-500
Mesh powder, and 12h is dried at 100 DEG C, the content of carbon is in carbon fiber enhancement resin base composite material micro mist
58.3%.
(3) micro mist forms
By the micro mist in 100g step (2), the porous nano alloy addition in 150g step (1) and 5g adhesive urea
Urea formaldehyde (being purchased from Jining Hua Kai resin Co., Ltd, article number HK-303) is thoroughly mixed, and is then placed in mold,
Under the pressure of 45MPa, compression molding, obtaining shape is spherical molding micro mist 255g, compactness 80%.
(4) phase transformation is handled
By molding micro mist obtained in (3), it is put into dedicated shock wave equipment, the air atmosphere in adjustment equipment makes oxygen in air
Content is 3%, at 2100 DEG C, under conditions of 40000MPa, carries out phase transformation processing to molding micro mist, generates diamond.Carbon
Fiber-reinforced resin matrix compound material micro mist be converted into diamond weight be 67.3CT, to resulting diamond into
The recycling steps such as row deposition, separation, collection, purifying, the weight of the diamond recycled are 62.8CT.
The carbon fiber enhancement resin base composite material conversion ratio of the present embodiment is 23.1%, and diamond yield is
93.3%.
Embodiment 2
(1) porous nano alloy addition is prepared
By weight be weight ratio by the first metal salt cobalt nitrate, the second metal salt cerous nitrate and hydrolytic reagent n-butanol it is 1:
0.1:15 mixing, is then vigorously stirred 0.5h at 80 DEG C, obtains the first mixture.Backward first mixture in partial size is added
Controlling agent ammonium chloride (concentration is 10 weight %), particle size controling agent ammonium chloride (in terms of N) and the molar ratio of hydrolytic reagent n-butanol are
1:2 after being added dropwise, continues to stir 2h at 80 DEG C, obtains the second mixture.Carrier oxidation is added into the second mixture again
Aluminium, on the basis of the first metal salt cobalt nitrate of 100 parts by weight, the dosage of aluminium oxide is 60 parts by weight, continues to stir at 100 DEG C
0.5h is mixed, then cools down, be filtered, washed, disperse resulting solid material on quartz plate, 800 DEG C of roastings 5 in Muffle furnace
Hour, the three-phase amorphous state porous nano alloy with micropore is obtained, micro-pore diameter is 0.5-5 μm.Then by resulting three-phase
Amorphous state porous nano alloy is uniformly mixed with elemental metals copper, the three-phase amorphous state porous nano alloy and elemental metals copper
Weight ratio be 1:25, handled 1 hour at 200 DEG C, obtain porous nano alloy addition.
(2) carbon fiber enhancement resin base composite material micro mist is prepared
Discarded carbon fiber enhancement resin base composite material is passed through cutting, is broken into molecule or is milled into 10-500
Mesh powder, and 12h is dried at 100 DEG C, the content of carbon is in carbon fiber enhancement resin base composite material micro mist
56.9%.
(3) micro mist forms
By the micro mist in 100g step (2), the porous nano alloy addition in 180g step (1) and 5g adhesive phenol
Urea formaldehyde (being purchased from 100,000 Chemical Co., Ltd. of Shandong, article number HK-0448) is thoroughly mixed, and is then placed in mold,
Under the pressure of 60MPa, compression molding, obtaining shape is spherical molding micro mist 258g, compactness 87%.
(4) phase transformation is handled
By molding micro mist obtained in (3), it is put into dedicated shock wave equipment, the air atmosphere in adjustment equipment makes oxygen in air
Content is 2.5%, at 2200 DEG C, under conditions of 45000MPa, carries out phase transformation processing to molding micro mist, generates diamond.
The weight that carbon fiber enhancement resin base composite material micro mist is converted into diamond is 65.2CT, to resulting diamond
The recycling steps such as deposited, separated, being collected, being purified, the weight of the diamond recycled is 61.2CT.
The carbon fiber enhancement resin base composite material conversion ratio of the present embodiment is 22.9%, and diamond yield is
93.9%.
Embodiment 3
(1) porous nano alloy addition is prepared
By the first metal salt nickelous carbonate, the second metal salt yttrium nitrate and hydrolytic reagent glycerine and isopropanol (molar ratio 4:
1) it is 1:0.15:25 mixing by weight being weight ratio, is then vigorously stirred 1.5h at 100 DEG C, obtains the first mixture.It
Particle size controling agent triethylenediamine, particle size controling agent triethylenediamine (in terms of N) and water are added in backward first mixture
The molar ratio for solving agent is 1:4, after being added dropwise, continues to stir 2h at 100 DEG C, obtains the second mixture.Again to the second mixing
Alumina catalyst support is added in object, on the basis of the first metal salt nickelous carbonate of 100 parts by weight, the dosage of aluminium oxide is 100 weight
Part, continue to stir 1h at 100 DEG C, then cools down, is filtered, washed, disperse resulting solid material on quartz plate, in horse
Not 800 DEG C roasting 5 hours in furnace, obtain the three-phase amorphous state porous nano alloy with micropore, and micro-pore diameter is 0.3-1 μm.
Then by resulting three-phase amorphous state porous nano alloy and elemental metals copper and elemental metals iron (weight ratio of copper and iron is 3:
2) weight ratio of uniformly mixing, the three-phase amorphous state porous nano alloy and elemental metals is 1:25, handles 1 at 200 DEG C
Hour, obtain porous nano alloy addition.
(2) carbon fiber enhancement resin base composite material micro mist is prepared
Discarded carbon fiber enhancement resin base composite material is passed through cutting, is broken into molecule or is milled into 10-500
Mesh powder, and 12h is dried at 100 DEG C, the content of carbon is in carbon fiber enhancement resin base composite material micro mist
57.2%.
(3) micro mist forms
By the micro mist in 100g step (2), the porous nano alloy addition in 200g step (1) and 2g adhesive urea
Urea formaldehyde (being purchased from Jining Hua Kai resin Co., Ltd, article number HK-303) is thoroughly mixed, and is then placed in mold,
Under the pressure of 50MPa, compression molding, obtaining shape is spherical molding micro mist 302g, compactness 84%.
(4) phase transformation is handled
By molding micro mist obtained in (3), it is put into dedicated shock wave equipment, the air atmosphere in adjustment equipment makes oxygen in air
Content is 3%, at 2200 DEG C, under conditions of 45000MPa, carries out phase transformation processing to molding micro mist, generates diamond.Carbon
Fiber-reinforced resin matrix compound material micro mist be converted into diamond weight be 71.8CT, to resulting diamond into
The recycling steps such as row deposition, separation, collection, purifying, the weight of the diamond recycled are 66.9CT.
The carbon fiber enhancement resin base composite material conversion ratio of the present embodiment is 25.1%, and diamond yield is
93.2%.
Embodiment 4
Carbon fiber enhancement resin base composite material is recycled according to the method for embodiment 1, difference is, step (3) are as follows: will
Micro mist in 100g step (2), the porous nano alloy addition in 50g step (1) and 5g adhesive Lauxite (are purchased from
Jining Hua Kai resin Co., Ltd, article number HK-303) it is thoroughly mixed, it is then placed in mold, in the pressure of 45MPa
Under, compression molding, obtaining shape is spherical molding micro mist 155g, compactness 80%.
The weight that the carbon fiber enhancement resin base composite material micro mist of the present embodiment is converted into diamond is 43.1CT,
Recycling steps, the weight of the diamond recycled such as deposited, separated, being collected, being purified to resulting diamond
Amount is 32.3CT.Carbon fiber enhancement resin base composite material conversion ratio is 14.8%, and diamond yield is 74.9%.
Embodiment 5
Carbon fiber enhancement resin base composite material is recycled according to the method for embodiment 1, difference is, step (3) are as follows: will
Micro mist in 100g step (2), the porous nano alloy addition in 500g step (1) and (purchase of 5g adhesive Lauxite
It is thoroughly mixed from Jining Hua Kai resin Co., Ltd, article number HK-303), mold is then placed in, in the pressure of 45MPa
Under, compression molding, obtaining shape is spherical molding micro mist 605g, compactness 80%.
The weight that the carbon fiber enhancement resin base composite material micro mist of the present embodiment is converted into diamond is 42.6CT,
Recycling steps, the weight of the diamond recycled such as deposited, separated, being collected, being purified to resulting diamond
Amount is 36.3CT.Carbon fiber enhancement resin base composite material conversion ratio is 14.6%, and diamond yield is 85.2%.
Comparative example 1
Carbon fiber enhancement resin base composite material is recycled according to the method for embodiment 1, and difference is, does not add porous nano
Alloy addition, but directly (have the micro mist in 100g step (2) purchased from Jining Hua Kai resin with 5g adhesive Lauxite
Limit company, article number HK-303) the step of being thoroughly mixed, being then pressed and molded, obtain shape be it is spherical at
Type micro mist 105g, compactness 75%, according still further to embodiment 1 carry out phase transformation processing the step of.
The weight that the carbon fiber enhancement resin base composite material micro mist of this comparative example is converted into diamond is 0.87CT,
Recycling steps, the weight of the diamond recycled such as deposited, separated, being collected, being purified to resulting diamond
Amount is 0.17CT.Carbon fiber enhancement resin base composite material conversion ratio is 0.3%, and diamond yield is 19.5%.
Comparative example 2
Recycle carbon fiber enhancement resin base composite material according to the method for embodiment 1, difference is, by metallic iron, cerium and
Aluminium is that 1:0.09:46 is mixed according to weight ratio, using mixed alloy as employed in additive alternate embodiment 1
Porous nano alloy addition.
The weight that the carbon fiber enhancement resin base composite material micro mist of this comparative example is converted into diamond is 9.0CT,
Recycling steps, the weight of the diamond recycled such as deposited, separated, being collected, being purified to resulting diamond
Amount is 4.9CT.Carbon fiber enhancement resin base composite material conversion ratio is 3.1%, and diamond yield is 54.4%.
Comparative example 3
Recycle carbon fiber enhancement resin base composite material according to the method for embodiment 1, difference is, by W metal, Mn, C,
Cr, Si, Ce and Fe are mixed into alloy powder, by weight percentage, ingredient are as follows: Ni:44.8 weight %, Mn:0.3 weight
Measure %, C:0.2 weight %, Cr:0.02 weight %, Si:0.02 weight %, Ce:0.06 weight %, surplus Fe, by above-mentioned conjunction
Bronze end is as porous nano alloy addition employed in additive alternate embodiment 1.
The weight that the carbon fiber enhancement resin base composite material micro mist of this comparative example is converted into diamond is 7.0CT,
Recycling steps, the weight of the diamond recycled such as deposited, separated, being collected, being purified to resulting diamond
Amount is 3.3CT.Carbon fiber enhancement resin base composite material conversion ratio is 2.4%, and diamond yield is 47.1%.
Testing example
According to diamond obtained by GB/T 19077.1-2003 method testing example 1-5 and comparative example 1-3
Particle diameter distribution tests its isostatic pressing strength according to JB/T 10985-2010 method, and the results are shown in Table 1.
Table 1
| Embodiment | Particle diameter distribution/μm | Isostatic pressing strength/Kgf |
| Embodiment 1 | 0.3-5 | 19.3 |
| Embodiment 2 | 0.1-3 | 18.6 |
| Embodiment 3 | 0.08-1 | 19.8 |
| Embodiment 4 | 0.05-0.7 | 13.8 |
| Embodiment 5 | 0.4-8 | 18.1 |
| Comparative example 1 | - | - |
| Comparative example 2 | 0.04-6 | 12.5 |
| Comparative example 3 | 0.02-7 | 11.3 |
By the comparing result of embodiment and comparative example as it can be seen that using disclosed method, there is special micropore by addition
It is higher can be changed into added value by the porous nano alloy addition of structure for discarded carbon fiber enhancement resin base composite material
Diamond, reduce the severe of changing condition, carbon fiber enhancement resin base composite material conversion ratio and artificial gold
Hard rock yield is higher, especially the weight ratio in carbon fiber enhancement resin base composite material micro mist and porous nano alloy addition
In 1:(1.5-2.5) when, the receipts of carbon fiber enhancement resin base composite material conversion ratio and diamond can be further increased
Rate.In addition, being had using the disclosed method recycling resulting diamond of carbon fiber enhancement resin base composite material relatively narrow
Particle diameter distribution and higher isostatic pressing strength, have preferable performance.
The preferred embodiment of the disclosure is described in detail above, still, during the disclosure is not limited to the above embodiment
Detail a variety of simple variants can be carried out to the technical solution of the disclosure in the range of the technology design of the disclosure, this
A little simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought, it should also be regarded as the disclosure of the present invention.
Claims (15)
1. a kind of method for recycling carbon fiber enhancement resin base composite material, which is characterized in that method includes the following steps:
A, carbon fiber enhancement resin base composite material is crushed be for partial size 10-500 mesh micro mist；
B, it is pressed and molded after mixing the micro mist obtained in step a with porous nano alloy addition, obtains molding micro mist,
It is 0.01-10 μm of micropore that the porous nano alloy addition, which has diameter,；
C, the molding micro mist obtained in step b is subjected to phase transformation processing, generates diamond；
The preparation step of the porous nano alloy addition includes:
(1) it is handled 0.5-3 hours at 60-120 DEG C after mixing the first metal salt, the second metal salt with hydrolytic reagent, obtains
One mixture, the metal in first metal salt are selected from least one of iron, copper, cobalt, tin, nickel and aluminium described second
Metal in metal salt is selected from least one of yttrium, lanthanum and cerium；
(2) first mixture obtained in step (1) is mixed with particle size controling agent, it is small that 1-6 is handled at 80-150 DEG C
When, obtain the second mixture；
(3) second mixture for obtaining step (2) is mixed with carrier, handles 0.5-3 hours at 80-150 DEG C, then
It is filtered, washed, resulting solid material is roasted 1-5 hours at 600-1000 DEG C, obtain the conjunction of three-phase amorphous state porous nano
Gold；
(4) three-phase amorphous state porous nano alloy obtained in step (3) is mixed with elemental metals, then in 150-
It is handled 1-2 hours at 250 DEG C, obtains porous nano alloy addition, the elemental metals are in iron, copper, cobalt, nickel and zinc
At least one.
2. according to the method described in claim 1, wherein, this method further include: in step a, the micro mist is dried
Step, the temperature of the drying are 80-150 DEG C, time 8-24h.
3. according to the method described in claim 1, wherein, in step (1), first metal salt, the second metal salt and hydrolysis
The weight ratio of agent is 1:(0.01-0.5): (1-30).
4. according to the method described in claim 1, wherein, in step (1), the hydrolytic reagent be selected from glycerine, isopropanol and
At least one of n-butanol.
5. according to the method described in claim 1, wherein, the particle size controling agent in step (2) with it is described in step (1)
The molar ratio of hydrolytic reagent is 1:(0.1-5).
6. according to the method described in claim 1, wherein, in step (2), the particle size controling agent is selected from ammonium hydroxide, hydroxide
At least one of sodium, ammonium chloride, acetamide, triethylenediamine, diethylenetriamines and isopropanolamine.
7. according to the method described in claim 1, wherein, in step (3), using first metal salt of 100 parts by weight as base
Standard, the dosage of the carrier are 30-200 parts by weight.
8. according to the method described in claim 1, wherein, in step (3), the carrier is selected from aluminium oxide, active carbon and layer
At least one of shape graphite.
9. according to the method described in claim 1, wherein, in step (4), the three-phase amorphous state porous nano alloy and simple substance
The weight ratio of metal is 1:(5-100).
10. according to the method described in claim 1, wherein, in step b, the weight of the micro mist and porous nano alloy addition
Amount is than being 1:(0.5-5).
11. according to the method described in claim 1, wherein, in step b, by the micro mist and porous nano alloy addition, glue
It is pressed and molded after glutinous agent mixing, obtains molding micro mist, on the basis of the micro mist of 100 parts by weight, the dosage of the adhesive
For 0.2-5 parts by weight, the adhesive is selected from least one of epoxy resin, phenolic resin and Lauxite.
12. according to the method described in claim 1, wherein, in step b, the pressure of the compression molding is 20-150MPa.
13. according to the method described in claim 1, wherein, the compactness of the molding micro mist obtained in step b be not less than
75%.
14. according to the method described in claim 1, wherein, the condition of the phase transformation processing in step c are as follows: oxygen in air atmosphere
Content is not more than 3%, and temperature is 2000-2500 DEG C, pressure 10000-100000MPa.
15. according to the method described in claim 1, wherein, the partial size of the diamond is 0.01-10 μm.
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