CN115353093A - Recycling method of polypropylene composite material for automobile - Google Patents
Recycling method of polypropylene composite material for automobile Download PDFInfo
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- CN115353093A CN115353093A CN202211020101.6A CN202211020101A CN115353093A CN 115353093 A CN115353093 A CN 115353093A CN 202211020101 A CN202211020101 A CN 202211020101A CN 115353093 A CN115353093 A CN 115353093A
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- 238000000034 method Methods 0.000 title claims abstract description 39
- -1 polypropylene Polymers 0.000 title claims abstract description 24
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
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- 239000000463 material Substances 0.000 claims abstract description 22
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
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- 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
A recycling method of polypropylene composite material for automobiles. The invention belongs to the field of recycling of polypropylene for vehicles. The invention aims to solve the technical problems that the existing toughening type polypropylene part for the vehicle is complex in structure and good in toughness, so that the crushing difficulty is high, the recovery process is complex, and the performance of the recovered PP is poor. The method comprises the following steps: cutting PP into small blocks; then adding sulfuric acid under a protective atmosphere, and carrying out high-temperature carbonization to obtain carbon powder; finally Ti is added 3 C 2 Nano Fe 3 O 4 Adding carbon powder and water into a reaction kettle for hydrothermal reaction to obtain MXene-Fe 3 O 4 Modified nanocarbon materialAnd (5) feeding. MXene-Fe 3 O 4 The modified nano carbon material is used for preparing a super capacitor and an electromagnetic shielding material.
Description
Technical Field
The invention belongs to the field of recycling of polypropylene for automobiles, and particularly relates to a recycling method of a polypropylene composite material for automobiles.
Background
The life cycle of the automobile is generally 8-15 years, each province and city is provided with a special mechanism for recycling and disassembling after the automobile is scrapped according to the national regulation, and except for repairing and recycling, other metal parts can be conveyed to a steel plant and an aluminum smelting enterprise for remelting and recycling. However, the non-metallic material member is difficult to handle. According to statistics of relevant departments, the varieties of the automotive plastics are sequentially PP, PVC, PU, unsaturated polyester, ABS, PF, PE, PA and composite materials according to the amount of the used plastics. Polypropylene is a typical partially crystalline thermoplastic resin, and its wide range of applications is determined by its good cost performance ratio. In recent years, with the rapid development of the automobile industry and the high performance of polypropylene products, the yield and demand of polypropylene have been greatly increased, and the polypropylene becomes the fastest growing plastic for automobiles in recent 10 years.
At present, a large amount of PP materials are used for automobiles, and can account for 30% of plastics of the whole automobiles. The method is characterized in that 300 million tons of PP is used in automobile production every year, but the recovery rate is less than 100 million tons, and the current process of polypropylene recovery comprises the steps of crushing, cleaning, rinsing, melting, adding a modifier or various catalysts for modification, and finally forming recovered PP granules through an extrusion process. Such a process flow has several disadvantages: firstly, the procedure is crushing, because parts using PP on an automobile, such as a bumper and a heat dissipation grid, have large volume and are complex and irregular in structure, the parts are difficult to put into a crusher and are difficult to enter the crusher; secondly, PP used on the automobile is reinforced and toughened plastic, so that the abrasion of a crusher cutter is great, the requirement on the abrasion resistance of the crusher cutter is very high, and the PP is difficult to finish; meanwhile, the whole recovery process is complicated, and the impurities can be removed only by cleaning and rinsing for several times. In addition, the performance of the produced recycled PP is poor, modification treatment is needed during use, and the use cost is increased.
Disclosure of Invention
The invention aims to solve the technical problems that the existing automotive toughened polypropylene part is complex in structure and good in toughness, so that the crushing difficulty is high, the recovery process is complex, and the performance of the recovered PP is poor, and provides a recycling method of an automotive polypropylene composite material.
One of the purposes of the invention is to provide a recycling method of a polypropylene composite material for an automobile, which comprises the following steps:
step 1: cutting a polypropylene (PP) part into small pieces;
step 2: adding sulfuric acid into the cut PP in a protective atmosphere, carrying out high-temperature carbonization, filtering, washing, drying and crushing to obtain carbon powder;
and step 3: mixing Ti 3 C 2 Nano Fe 3 O 4 Adding carbon powder and water into a reaction kettle, heating after ultrasonic oscillation for hydrothermal reaction to obtain MXene-Fe 3 O 4 A modified nanocarbon material.
Further defined, step 1 is cutting using a laser cutter.
Further limiting, the size of the small block in the step 1 is 10-15cm 3 。
Further limiting, the mass ratio of the sulfuric acid to the PP in the step 2 is (3-3.5): 1.
further limiting, the high-temperature carbonization in the step 2 is a staged heating carbonization.
Further limited, the step-type temperature-rising carbonization process:
adding sulfuric acid, heating to 250-350 deg.C, maintaining for 2-3h, heating to 1800-2200 deg.C, and maintaining for 5-6h.
Further defined, step 3 is Ti 3 C 2 Nano Fe 3 O 4 And the mass ratio of the carbon powder to the water is 1: (1.5-2.5): (3.5-4.5): (100-120).
Further limiting, the ultrasonic frequency in the step 3 is 230-250Hz, and the time is 25-35min.
Further limiting, the hydrothermal reaction temperature in the step 3 is 100-200 ℃ and the time is 5-7h.
Another object of the present invention is to provide MXene-Fe prepared by the above method 3 O 4 A modified nanocarbon material.
The invention also aims to provide MXene-Fe prepared by the method 3 O 4 The modified nano carbon material is applied to super capacitors and electromagnetic shielding materials.
Compared with the prior art, the invention has the advantages that:
1) According to the invention, a high-temperature carbonization method is adopted to convert PP into the porous carbon material, the surface of the porous carbon material contains a large number of oxygen-containing functional groups, the material compatibility is better, and the material application is more flexible due to the large number of functional groups, the material performances such as sound, light, electricity and the like can be realized by various modification means, and the porous carbon material has wider application scenes.
2) The invention adopts a staged heating carbonization mode, keeps the temperature for a period of time at low temperature, decomposes the additive in the composite material into gas for volatilization, simultaneously, the sulfuric acid can corrode and remove the glass fiber in the waste composite material in a heating state, and then the temperature is continuously raised for carbonization, at the moment, the sulfuric acid accelerates the dehydration and carbonization of the polypropylene.
3) During the reaction, fe 3 O 4 And MXene coupling under electrostatic action, fe 3 O 4 Can reduce MXene surface energy and meanwhile Ti is generated in the reaction process 3 C 2 React with a plurality of functional groups on the surface of the porous nano carbon material to lead Ti to react 3 C 2 Attached to the surface of the nano carbon, the surface activity and the conductivity of the nano carbon material are improved.
Drawings
FIG. 1 shows MXene-Fe obtained in example 1 3 O 4 XRD pattern of modified nanocarbon material;
FIG. 2 shows MXene-Fe obtained in example 1 3 O 4 SEM images of modified nanocarbon materials;
FIG. 3 shows MXene-Fe obtained in example 1 3 O 4 Modified nanocarbonTEM images of the material.
Detailed Description
The first embodiment is as follows: the recycling method of the polypropylene composite material for the automobile of the embodiment comprises the following steps:
step 1: cutting a polypropylene (PP) part into small pieces;
and 2, step: adding sulfuric acid into the cut PP under the protective atmosphere, carrying out high-temperature carbonization, filtering, washing, drying and crushing to obtain carbon powder;
and step 3: mixing Ti 3 C 2 Nano Fe 3 O 4 Adding carbon powder and water into a reaction kettle, heating after ultrasonic oscillation for hydrothermal reaction to obtain MXene-Fe 3 O 4 A modified nanocarbon material.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is:
Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is:
Other steps and parameters are the same as those in the first embodiment.
The fourth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is:
Other steps and parameters are the same as those in the first embodiment.
The fifth concrete implementation mode is as follows: the first difference between the present embodiment and the specific embodiment is:
in the step 2, the mass ratio of the sulfuric acid to the PP is (3-3.5): 1.
other steps and parameters are the same as those in the first embodiment.
The sixth specific implementation mode: the first difference between the present embodiment and the specific embodiment is:
in the step 2, the mass ratio of the sulfuric acid to the PP is 3:1.
other steps and parameters are the same as those in the first embodiment.
The seventh embodiment: the first difference between the present embodiment and the specific embodiment is:
and 2, the high-temperature carbonization is staged temperature-rising carbonization.
Other steps and parameters are the same as those in the first embodiment.
The specific implementation mode eight: the seventh embodiment is different from the seventh embodiment in that:
the staged temperature-rising carbonization process comprises the following steps:
adding sulfuric acid, heating to 250-350 deg.C, maintaining for 2-3h, heating to 1800-2200 deg.C, and maintaining for 5-6h.
Other steps and parameters are the same as those in the seventh embodiment.
The specific implementation method nine: the first difference between the present embodiment and the specific embodiment is:
step 3 of Ti 3 C 2 Nano Fe 3 O 4 And the mass ratio of the carbon powder to the water is 1: (1.5-2.5): (3.5-4.5): (100-120).
Other steps and parameters are the same as those in the first embodiment.
The detailed implementation mode is ten: the first difference between the present embodiment and the specific embodiment is:
step 3 of Ti 3 C 2 Nano Fe 3 O 4 And the mass ratio of the carbon powder to the water is 1:2:4:100.
other steps and parameters are the same as those in the first embodiment.
The concrete implementation mode eleven: the first difference between the present embodiment and the specific embodiment is:
in step 3, the ultrasonic frequency is 230-250Hz, and the time is 25-35min.
Other steps and parameters are the same as those in the first embodiment.
The specific implementation mode twelve: the first difference between the present embodiment and the specific embodiment is:
in the step 3, the ultrasonic frequency is 240Hz, and the time is 30min.
Other steps and parameters are the same as those in the first embodiment.
The specific implementation mode is thirteen: the first difference between the present embodiment and the specific embodiment is:
the hydrothermal reaction temperature in the step 3 is 100-200 ℃ and the time is 5-7h.
Other steps and parameters are the same as those in the first embodiment.
The specific implementation mode is fourteen: the first difference between the present embodiment and the specific embodiment is:
in the step 3, the hydrothermal reaction temperature is 150 ℃ and the time is 6 hours.
Other steps and parameters are the same as those in the first embodiment.
The concrete implementation mode is fifteen: MXene-Fe prepared by recycling method of polypropylene composite material for automobile in embodiment 3 O 4 A modified nanocarbon material.
The MXene-Fe 3 O 4 The modified nano carbon material has an accordion-like structure, and larger gaps exist among layers.
The specific implementation mode is sixteen: MXene-Fe prepared by recycling method of polypropylene composite material for automobile in embodiment 3 O 4 The modified nano carbon material is applied to super capacitors and electromagnetic shielding materials.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates that the singular form is clear
Example 1: the recycling method of the polypropylene composite material for the automobile comprises the following steps:
step 1: cutting a polypropylene (PP) part to a size of 15cm using a laser cutting machine 3 Small pieces of (2);
step 2:
s1: under the nitrogen atmosphere, 15Kg of sulfuric acid with the concentration of 98 percent is added into 5Kg of cut PP;
s2: and (3) carrying out staged temperature rise carbonization, wherein the specific process of the staged temperature rise carbonization comprises the following steps:
adding sulfuric acid, heating to 300 deg.C, maintaining for 2 hr, heating to 2000 deg.C, maintaining for 6 hr,
s3: filtering;
s4: washing with deionized water for 3 times;
s5: oven drying at 200 deg.C for 30min;
s6: pulverizing to particle size of 50 μm to obtain carbon powder;
and step 3:
s1: 1gTi 3 C 2 2g of nano Fe 3 O 4 Adding 4g of carbon powder and 100g of water into a reaction kettle;
s2: ultrasonic oscillation: oscillating for 30min under 240 Hz;
s3: carrying out hydrothermal reaction for 6h at 150 ℃ to obtain MXene-Fe 3 O 4 A modified nanocarbon material.
Detection test
FIG. 1 shows MXene-Fe obtained in example 1 3 O 4 XRD pattern of modified nanocarbon materials.
As can be seen from FIG. 1, ti 3 AlC 2 -MAX has a characteristic peak at 2 θ =9.6 °, corresponding to the (002) crystal plane. And it also has a characteristic peak at 2 θ =39 ° corresponding to the (008) crystal plane. After reaction, a plurality of layers of Ti 3 C 2 T x The peaks of-MXene at 2 θ =9.6 ° and 2 θ =39 ° disappear, and in contrast, there is a multilayer Ti3C2 characteristic peak at 2 θ =9.0 °. Evidence of MXene-Fe 3 O 4 The modified nano carbon material is successfully prepared.
FIG. 2 shows MXene-Fe obtained in example 1 3 O 4 SEM images of modified nanocarbon materials.
As can be seen from FIG. 2, MXene-Fe 3 O 4 The modified nano carbon material has an accordion-like structure, and large gaps exist among layers.
FIG. 3 shows MXene-Fe obtained in example 1 3 O 4 TEM images of modified nanocarbon materials.
As can be seen from FIG. 3, fe 3 O 4 Composite Ti 3 C 2 The back surface is wrinkled and largeAnd (5) measuring black spots. The black spots produced were mainly Fe 3 O 4 Black round spot under transmission electron microscope, and the reason for surface wrinkle is Fe 3 O 4 Is composited in Ti 3 C 2 T x The MXene surface causes its surface energy to increase, resulting in surface wrinkles.
While the invention has been described with reference to specific preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and alternative embodiments, which may be apparent to those skilled in the art, within the spirit and scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The recycling method of the polypropylene composite material for the automobile is characterized by comprising the following steps:
step 1: cutting the PP part into small blocks;
step 2: adding sulfuric acid into the cut PP under the protective atmosphere, carrying out high-temperature carbonization, filtering, washing, drying and crushing to obtain carbon powder;
and step 3: mixing Ti 3 C 2 Nano Fe 3 O 4 Adding carbon powder and water into a reaction kettle, heating after ultrasonic oscillation for hydrothermal reaction to obtain MXene-Fe 3 O 4 A modified nanocarbon material.
2. The method according to claim 1, wherein step 1 is performed by cutting with a laser cutter, and the size of the small block is 10-15cm 3 。
3. The process according to claim 1, wherein the mass ratio of sulfuric acid to PP in step 2 is (3-3.5): 1.
4. the method according to claim 1, wherein the high-temperature carbonization in step 2 is a stepwise elevated-temperature carbonization.
5. The method according to claim 4, characterized in that the staged temperature-rising carbonization process: adding sulfuric acid, heating to 250-350 deg.C, maintaining for 2-3h, heating to 1800-2200 deg.C, and maintaining for 5-6h.
6. The method of claim 1, wherein Ti in step 3 3 C 2 Nano Fe 3 O 4 The mass ratio of the carbon powder to the water is 1: (1.5-2.5): (3.5-4.5): (100-120).
7. The method according to claim 1, wherein the ultrasonic frequency in step 3 is 230-250Hz and the time is 25-35min.
8. The method according to claim 1, wherein the hydrothermal reaction temperature in step 3 is 100-200 ℃ and the time is 5-7h.
9. MXene-Fe obtained by the process of any one of claims 1 to 8 3 O 4 A modified nanocarbon material.
10. MXene-Fe obtainable by the process according to any one of claims 1 to 8 3 O 4 The modified nano carbon material is applied to super capacitors and electromagnetic shielding materials.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211020101.6A CN115353093A (en) | 2022-08-24 | 2022-08-24 | Recycling method of polypropylene composite material for automobile |
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| CN202211020101.6A CN115353093A (en) | 2022-08-24 | 2022-08-24 | Recycling method of polypropylene composite material for automobile |
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