CN114715881B - Waste plastic derived nano porous carbon material and preparation method and application thereof - Google Patents
Waste plastic derived nano porous carbon material and preparation method and application thereof Download PDFInfo
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- CN114715881B CN114715881B CN202210338901.6A CN202210338901A CN114715881B CN 114715881 B CN114715881 B CN 114715881B CN 202210338901 A CN202210338901 A CN 202210338901A CN 114715881 B CN114715881 B CN 114715881B
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- 229920003023 plastic Polymers 0.000 title claims abstract description 116
- 239000004033 plastic Substances 0.000 title claims abstract description 116
- 239000002699 waste material Substances 0.000 title claims abstract description 114
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004800 polyvinyl chloride Substances 0.000 claims description 57
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 229920000877 Melamine resin Polymers 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 30
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 30
- 239000007833 carbon precursor Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- OTUXCLKRSRDYPV-UHFFFAOYSA-N acetylene hydrochloride Chemical compound Cl.C#C OTUXCLKRSRDYPV-UHFFFAOYSA-N 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000005997 Calcium carbide Substances 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 15
- 238000000197 pyrolysis Methods 0.000 description 13
- 239000011148 porous material Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005695 dehalogenation reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000007038 hydrochlorination reaction Methods 0.000 description 5
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/40—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
-
- 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
Abstract
The invention discloses a waste plastic derived nano porous carbon material and a preparation method and application thereof. The waste plastic derived nano porous carbon material and the preparation method thereof provided by the invention not only can change waste into valuable, but also are simple in production process, are environment-friendly technologies, accord with national policies about recycling of wastes, and are rich in nitrogen elements and defects, can meet the requirements when being used as a catalyst, can be used as the catalyst for producing vinyl chloride monomer by a calcium carbide method, and can also be used as a capacitor and electrode material-based adsorption material.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a waste plastic derived nano porous carbon material and a preparation method thereof.
Background
Halogen-containing waste plastics are one of the most productive plastics in the world and the most widely used plastics, and have wide application in the fields of construction, packaging, electrical and service industries, etc. Polyvinyl chloride (PVC) is a typical waste plastic, and the polyvinyl chloride output of China in 2020 reaches 2074 ten thousand tons, and the apparent consumption is 2107 ten thousand tons, which is the first worldwide. However, with the rapid increase of the consumption of halogen-containing waste plastic products and the continuous enhancement of environmental awareness, the treatment and recycling of waste halogen-containing plastics have attracted great attention. Traditional methods for treating waste halogen-containing plastics include burial, mechanical grinding into small fragments or degradation into chemical small molecules, and incineration, which are not only a waste of resources but also a great hazard to the environment.
The waste plastic has the characteristics of high carbon content, less impurities and the like, so that the waste plastic can become an excellent raw material for preparing carbon materials and is an ideal carbonization precursor. The waste halogen-containing plastic is converted into the nano porous carbon material with high added value, so that the problem of environmental pollution caused by the waste halogen-containing plastic can be solved to a certain extent. However, the preparation of carbon materials directly from halogen-containing plastics is a challenging task. Taking polyvinyl chloride waste plastics as an example, polyvinyl chloride is taken as a high-molecular polymer with high thermoplasticity, melting is started at 180 ℃, and decomposition is started at 220 ℃ to generate HCl, and the generation of HCl promotes the decomposition of the polyvinyl chloride to generate liquid or gas olefin, so that a carbon material cannot be obtained by using a traditional pyrolysis method or the carbon yield is extremely low. Meanwhile, halogen elements such as chlorine in waste plastics can generate organic matters such as dioxin in the pyrolysis process, and can bring great harm to the environment. The existence of these problems limits the use of waste plastics as carbon precursors in the production of carbon.
In recent years, researchers have disclosed methods of preparing some plastic-derived carbon materials. Patent CN107381532A and CN111217353A respectively prepare a polyvinyl chloride-based carbon pellet and carbon powder by using polyvinyl chloride as raw materials through treatment methods such as catalytic dechlorination, crosslinking solidification and pyrolysis, and the like, and the specific morphology of the pellet and the carbon powder has wide application prospects in the fields of catalysis, electrochemistry and adsorption separation. Patent CN108658055A discloses a method for preparing porous carbon by recycling waste polyvinyl chloride products, and the preparation of the catalyst mainly comprises Mg (OH) 2 As a template, waste polyvinyl chloride products are prepared into porous carbon materials through the preparation steps of carbonization, acid washing and the like. The patent CN101208842A and the patent CN102800489A respectively take polyvinyl chloride, polyvinylidene chloride (PVDC) and polyvinylidene fluoride (PVDF) as raw materials, and a KOH activation method is adopted to prepare the carbon material with high specific surface area. Although the carbon materials with rich pore structures can be prepared by the methods, the further application of the carbon materials is limited by the defects of complex preparation process, harsh preparation conditions and the like because complex steps of acid washing, template removal, strong alkali activation and the like are required. The patent CN103183345A takes chlorine-containing organic polymer plastic as a carbon source, organic amine as a nitrogen source, and dechlorination is carried out at 400 ℃ in the presence of an activator (phosphoric acid and strong alkali) to obtain the nitrogen-doped active carbon with high specific surface area. Although the method obtains a nitrogen-rich carbon material, the process is complex, and the preparation can be completed with the aid of various activators, so that the preparation cost is increased, and certain corrosion is brought to equipment due to the use of the activators. At the same time, the chlorine-containing high molecular organic matters are subjected to dechlorination at the temperature of 100-300 ℃ to inevitably generate chlorine-containing dioxin and other organic matters, and the substances can bring great harm to the environment without effective treatment.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing a nano porous carbon material by pyrolysis of waste plastics assisted by environment-friendly melamine, which has simple process and can effectively remove chlorine element in the waste plastics. The invention directly takes waste plastic as raw material, takes melamine as nitrogen source and dechlorinating agent, adopts room temperature mechanical ball milling method to crosslink and dechlorinate, and then prepares the product by heat treatment method. The method takes the plastic as the raw material, greatly reduces the preparation cost of the material, and the plastic and melamine are mixed for normal-temperature dehalogenation, so that the corrosion resistance requirements of equipment before and after subsequent carbonization are reduced, and the prepared nano porous carbon has a nano sheet structure.
The invention defines a preparation method of a waste plastic derived nano porous carbon material, which is characterized by comprising the following steps: 1) Crushing waste plastics into powder, adding the powder, a solvent and melamine into a ball milling tank for grinding reaction to obtain a porous carbon precursor mixture;
2) Washing the porous carbon precursor obtained in the step 1) with deionized water, removing halogen-containing substances in the mixture, and drying to obtain the porous carbon precursor;
3) And (3) carrying out heat treatment on the porous carbon precursor obtained in the step (2) under the protection of inert atmosphere at a certain temperature, and naturally cooling to room temperature to obtain the waste plastic-derived nano porous carbon material.
Furthermore, the invention also defines that the waste plastic is halogen-containing waste plastic, preferably polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, chlorinated polyolefin, chlorinated rubber and chlorinated polypropylene, and the mass ratio of the waste plastic to melamine is 1:0.5-2.
Further, the invention also defines that the solvent in step 1) is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, cyclohexanone; the grinding method is manual grinding or ball milling; during ball milling, the ball ratio is 1: 5-15, the ball milling rotating speed is 400-600 rpm, and the ball milling time is 1-4 h.
Further, the invention also defines that the drying temperature in the step 2) is 70-120 ℃ and the drying time is 8-12 h.
Further, the invention also defines the heat treatment process in step 3) as follows: heating to 600-1000 ℃ at a heating rate of 5-10 ℃/min, roasting at constant temperature for 1-2 h for carbonization, and naturally cooling to room temperature after carbonization to obtain the waste plastic derived nano porous carbon material; the inert gas is nitrogen, argon or helium, and the flow rate of the inert gas is 30-100 mL/min.
Further, the invention also definesThe waste plastic derived nano porous carbon material obtained by the limited preparation method has a nitrogen-rich and defect-rich structure, the nitrogen content is 8-30wt% and the specific surface area is 30-700m 2 /g。
The invention also defines the application of the specific waste plastic derived nano porous carbon material obtained by the limiting method as a carbon-based nonmetallic catalyst in the reaction of preparing chloroethylene from acetylene and hydrogen chloride; the acetylene hydrochlorination reaction is carried out by conventional procedures, for example by:
the hydrochlorination of acetylene was carried out in a stainless steel fixed bed reactor with an internal diameter of 10mm, a catalyst loading of 2mL, acetylene and hydrogen chloride pressures of 0.1MPa, n (C) 2 H 2 ) N (HCl) =1.2, and the space velocity of acetylene flow is controlled to be 60h -1 The reaction temperature is 220 ℃, and the acetylene gas is purified to remove H through concentrated sulfuric acid 2 S and H 3 P and other impurities, and the hydrogen chloride gas is dehydrated by a dryer of silica gel. Before the reaction, nitrogen is used for purging to remove water and air in the system, and then acetylene and hydrogen chloride gas are simultaneously introduced for reaction for 30 hours; the gas flow is controlled by a mass flow meter. The reaction product was subjected to gas chromatography analysis after absorbing hydrogen chloride gas with sodium hydroxide solution, and the content of each component was measured using an area normalization method.
The principle of the invention is as follows: according to the invention, melamine is used as a nitrogen source and a dehalogenation agent, during the grinding process, the melamine molecules and the halogens of polymer molecules in waste plastics are subjected to a coupling reaction to generate hydrogen halide, the removed hydrogen halide is washed by deionized water and is removed in a solution form, and finally a crosslinked reticular molecular structure is formed, and the crosslinked reticular molecular structure is more stable than the chain structure of the chlorine-containing polymer, so that the subsequent pyrolysis process can be tolerated, and the carbon yield is greatly improved; the reaction removes 99.9% of halogen elements, and melamine which is not successfully crosslinked with halogen polymers in the pyrolysis process can be decomposed to generate volatile components and plays a role in pore forming, so that the finally obtained carbon material has a rich pore structure, and simultaneously, nitrogen atoms and carbon atoms are removed in the pyrolysis process, so that the finally formed nano porous carbon has the characteristics of being rich in nitrogen and defects.
By adopting the technology, compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, waste plastics such as household garbage PVC, PVDC, PVDF are used as raw materials, low-cost melamine is used as a dehalogenation agent and a nitrogen source, crosslinking of polyvinyl chloride and melamine is realized through mechanical ball milling, removal of hydrogen chloride is completed, and a carbon precursor after crosslinking and curing is subjected to high-temperature pyrolysis to obtain a carbon material rich in nitrogen and defects; the halogen element is maximally removed in the form of hydrogen chloride or hydrogen fluoride during crosslinking, so that toxic substances, namely halogen elements, in waste plastics are effectively removed, the problem of secondary pollution to the environment caused by the generation of dioxin in the pyrolysis process is solved, the cost is low, the condition is milder, the process is simple, the corrosion of a dehalogenating agent (strong alkali or metal oxide) to equipment in the dehalogenation process in the conventional method is avoided, the industrial production is inspired, and meanwhile, the biomass charcoal generated by co-pyrolysis of the waste plastics and melamine is higher in yield and better in quality, and the subsequent scientific and industrial research is facilitated;
2) The invention realizes the normal temperature dehalogenation of the halogen-containing waste plastics by a limited method, the removed halogen can be washed by water under the normal temperature condition, the generation of dioxin in the pyrolysis process is avoided, the carbon yield of the final waste plastic derived carbon material is high, and the problem of low carbon production yield of the halogen-containing plastics is solved;
3) The waste plastic derived nano porous carbon material prepared by the method spontaneously introduces rich pore structures in the pyrolysis process, does not need to add an activating agent and a template agent, does not need an acid washing process, avoids the problems of equipment loss, waste acid treatment and the like in the acid washing process, greatly reduces the preparation process of the material and reduces the cost;
4) The method for preparing the plastic-derived nano porous carbon material not only can change waste into valuable, but also has simple production process, is a green and environment-friendly technology, accords with national policy about recycling of wastes, and has rich nitrogen elements and defects, and the carbon yield of the obtained waste plastic-derived nano porous carbon material can reach more than 23 percentThe content is 8-30wt%, and the specific surface area is more than 30-700m 2 /g; can meet the requirements when the catalyst is used as a catalyst, can be used as the catalyst for producing vinyl chloride monomer by a calcium carbide method, can also be used as an adsorption material and an electrode material, and has wide application prospect in catalysis, adsorption and electrochemistry.
Drawings
FIG. 1 is a scanning electron microscope image of a polyvinyl chloride waste plastic-derived nanoporous carbon material obtained in example 1;
FIG. 2 is a scanning electron microscope image of activated carbon;
FIG. 3 is a drawing showing nitrogen physical absorption of the polyvinyl chloride waste plastic-derived nanoporous carbon material obtained in example 1;
FIG. 4 is a graph showing pore size distribution of a polyvinyl chloride waste plastic-derived nanoporous carbon material obtained in example 1;
FIG. 5 is a nitrogen Raman diagram of the polyvinyl chloride waste plastic-derived nanoporous carbon material obtained in example 1;
FIG. 6 is a Raman diagram of comparative column 2 activated carbon;
FIG. 7 is a thermogravimetric view of polyvinyl chloride, melamine and polyvinyl chloride waste plastic derived nanoporous carbon precursors;
FIG. 8 is a graph showing the evaluation of the activities of the resulting polyvinyl chloride waste plastic-derived nanoporous carbon material and activated carbon of example 1.
Detailed Description
The invention will be further illustrated by the following examples, without limiting the scope of the invention thereto.
Example 1 a method for preparing a waste plastic-derived nanoporous carbon material, comprising the following steps:
(1) Taking a polyvinyl chloride waste plastic handbag, and putting the polyvinyl chloride waste plastic handbag into a crusher for crushing to obtain polyvinyl chloride waste plastic powder;
(2) Respectively weighing 10g of melamine and 10g of polyvinyl chloride waste plastic powder in a ball milling tank, adding 20mLN, N-dimethylformamide and 200g of stainless steel balls, and ball milling for 4 hours at a rotating speed of 500 rpm to obtain a mixed product;
(3) Washing the mixed product with deionized water, and drying at 100 ℃ for 10 hours to obtain a porous carbon precursor;
(4) Placing the porous carbon precursor into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere (the flow rate of nitrogen is 50mL/min and the inert gas conditions of examples 3-8 are the same), roasting for 2 hours, and naturally cooling to room temperature to obtain the polyvinyl chloride waste plastic derivative nano porous carbon material, wherein the carbon yield is as follows: 13.1%, nitrogen content: 13.5wt% specific surface area: 307m 2 And/g. The scanning electron microscope, the nitrogen physical absorption drawing, the aperture distribution diagram and the nitrogen raman diagram of the product obtained in the embodiment are respectively shown in fig. 1, 3, 4 and 5, the scanning electron microscope and the raman diagram of the activated carbon are respectively shown in fig. 2 and 6, and as can be seen from fig. 1 and 2, the particle stacking structure of the product is different from that of the activated carbon: the polyvinyl chloride waste plastic derived nano porous carbon material of the embodiment is in a nano sheet shape; as can be seen from fig. 3 and 4, the polyvinyl chloride waste plastic-derived nanoporous carbon material of the present embodiment has a multi-stage pore structure; as can be seen from FIGS. 5 and 6, the polyvinyl chloride waste plastic-derived nanoporous carbon material of the embodiment has a rich defect structure, I D /I G :2.09; the thermogravimetric chart of the polyvinyl chloride, melamine and the polyvinyl chloride waste plastic derived nanoporous carbon precursor obtained in this example is shown in fig. 7, and it can be seen from fig. 7 that the polyvinyl chloride and melamine are pyrolyzed under high temperature condition, and finally no carbon is produced, and the polyvinyl chloride can be carbonized successfully with the aid of melamine to obtain the final product of the polyvinyl chloride waste plastic derived nanoporous carbon material.
Example 2a method for preparing a waste plastic-derived nanoporous carbon material, comprising the following steps:
(1) Taking a polyvinyl chloride waste plastic handbag, and putting the polyvinyl chloride waste plastic handbag into a crusher for crushing to obtain polyvinyl chloride waste plastic powder;
(2) Respectively weighing 5g of melamine and 10g of polyvinyl chloride waste plastic powder in a ball milling tank, adding 20mL of tetrahydrofuran, adding 225g of stainless steel balls, and then ball milling for 2 hours at a rotating speed of 600 rpm to obtain a mixed product;
(3) Washing the mixed product with deionized water, and drying at 80 ℃ for 12 hours to obtain a porous carbon precursor;
(4) Placing the porous carbon precursor into a tubular furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under helium atmosphere (the flow rate of helium is 100 mL/min), roasting for 1h, and naturally cooling to room temperature to obtain the polyvinyl chloride waste plastic derivative nano porous carbon material, wherein the carbon yield is as follows: 17.8%, nitrogen content: 8.8wt% of specific surface area: 193m 2 /g。
Example 3a method for preparing a waste plastic-derived nanoporous carbon material, comprising the following steps:
(1) Taking a polyvinyl chloride waste plastic handbag, and putting the polyvinyl chloride waste plastic handbag into a crusher for crushing to obtain polyvinyl chloride waste plastic powder;
(2) Respectively weighing 20g of melamine and 10g of polyvinyl chloride waste plastic powder in a ball milling tank, adding 20mLN, N-dimethylformamide, adding 300g of stainless steel balls, and then ball milling for 4 hours at a rotating speed of 500 rpm to obtain a mixed product;
(3) Washing the mixed product with deionized water, and drying at 100 ℃ for 10 hours to obtain a porous carbon precursor;
(4) Placing the porous carbon precursor into a tube furnace, heating to 600 ℃ at a heating rate of 8 ℃/min under nitrogen atmosphere, roasting for 2 hours, and naturally cooling to room temperature to obtain the polyvinyl chloride waste plastic derivative nano porous carbon material, wherein the carbon yield is as follows: 11.5%, nitrogen content: 29.9wt%, specific surface area: 37m 2 /g。
Example 4 preparation method of waste plastic derived nanoporous carbon material, comprising the following steps:
(1) Respectively weighing 5g of melamine and 10g of polyvinylidene chloride powder, adding 20mLN, N-dimethylformamide into a ball milling tank, adding 150g of stainless steel balls, and then ball milling for 4 hours at a rotating speed of 500 rpm to obtain a mixed product.
(2) Washing the mixed product with deionized water, and drying at 100 ℃ for 10 hours to obtain a porous carbon precursor;
(3) Placing the porous carbon precursor into a tubular furnace, purging the air in the tubular furnace at room temperature with the flow rate of nitrogen being 50mL/min under the nitrogen atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min for roasting for 2 hours, and naturally cooling toObtaining the polyvinylidene chloride waste plastic derived nano porous carbon material at room temperature, and obtaining the carbon yield: 13%, nitrogen content: 13.4wt% specific surface area: 726m 2 /g。
Example 5 preparation method of waste plastic derived nanoporous carbon material, comprising the following steps:
(1) Respectively weighing 5g of melamine and 10g of chlorinated polypropylene waste plastic powder, adding 20mLN, N-dimethylformamide into a ball milling tank, adding 200g of stainless steel balls, and then ball milling for 2 hours at a rotating speed of 500 rpm to obtain a mixed product;
(2) Washing the mixed product with deionized water, and drying at 120 ℃ for 8 hours to obtain a porous carbon precursor;
(3) Placing the porous carbon precursor into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, roasting for 2 hours, and naturally cooling to room temperature to obtain the chlorinated polypropylene waste plastic derivative nano porous carbon material, wherein the carbon yield is as follows: 20.3%, nitrogen content: 10.5wt% specific surface area: 286m 2 /g。
Example 6 preparation method of waste plastic-derived nanoporous carbon material, comprising the following steps:
(1) 10g of melamine and 10g of chlorinated rubber waste plastic powder are respectively weighed and put into a ball milling tank, 20mLN, N-dimethylformamide and 200g of stainless steel balls are added, and ball milling is carried out for 4 hours at a rotating speed of 500 revolutions per minute, so that a mixed product is obtained.
(2) Washing the mixed product with deionized water, and drying at 100 ℃ for 8 hours to obtain a porous carbon precursor;
(3) Placing the porous carbon precursor into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, roasting for 2 hours, and naturally cooling to room temperature to obtain the chlorinated rubber waste plastic derivative nano porous carbon material, wherein the carbon yield is as follows: 24.3%, nitrogen content: 13.2wt% specific surface area: 289m 2 /g。
Example 7 a method for preparing a waste plastic-derived nanoporous carbon material, comprising the steps of:
(1) Taking a polyvinyl fluoride waste plastic handbag, and putting the handbag into a crusher for crushing to obtain polyvinyl fluoride waste plastic powder;
(2) Respectively weighing 10g of melamine and 10g of polyvinyl chloride waste plastic powder in a ball milling tank, adding 20mL of cyclohexanone, adding stainless steel balls with the total mass of 50g, and then ball milling for 4 hours at a rotating speed of 400 rpm to obtain a mixed product;
(3) Washing the mixed product obtained in the step (2) with deionized water, removing HCl removed in the step (2), and drying at 120 ℃ for 9 hours to obtain a porous carbon precursor;
(4) Placing the porous carbon precursor obtained in the step (3) into a tubular furnace, purging and removing air in the tubular furnace at room temperature with the flow rate of nitrogen being 50mL/min under the nitrogen atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min, roasting for 2 hours, and naturally cooling to room temperature to obtain the polyvinyl fluoride waste plastic derivative nano porous carbon material, wherein the carbon yield is as follows: 9.5%, nitrogen content: 8.7wt% of specific surface area: 125m 2 /g, pore volume: 0.2cm 3 g -1 ，I D /I G :1.35, bulk density: 0.25kg/m 3 。
Example 8 preparation method of waste plastic-derived nanoporous carbon material, comprising the following steps:
(1) Taking a polyvinyl chloride waste plastic handbag, and putting the polyvinyl chloride waste plastic handbag into a crusher for crushing to obtain polyvinyl chloride waste plastic powder;
(2) Respectively weighing 12g of melamine and 8g of polyvinyl chloride waste plastic powder in a ball milling tank, adding 20mLN, N-dimethylformamide, adding stainless steel balls with the total mass of 200g, and then ball milling for 4 hours at a rotating speed of 500 rpm to obtain a mixed product;
(3) Washing the mixed product obtained in the step (2) with deionized water, removing HCl removed in the step (2), and drying at 100 ℃ for 10 hours to obtain a porous carbon precursor;
(4) Placing the porous carbon precursor obtained in the step (3) into a tubular furnace, purging and removing air in the tubular furnace at room temperature with the flow rate of argon of 50mL/min under the nitrogen atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min, roasting for 1h, and naturally cooling to room temperature to obtain the polyvinyl chloride waste plastic derivative nano porous carbon material, wherein the carbon yield is as follows: 14.0%, nitrogen content: 13.4wt% specific surface area: 278m 2 /g, pore volume: 0.5cm 3 g -1 ，I D /I G :1.97, bulk density: 0.15kg/m 3 。
Comparative example 1
In comparison with example 1, the effect of melamine on polyvinyl chloride-derived carbon materials was investigated without the addition of melamine
(1) Taking a polyvinyl chloride waste plastic handbag, and putting the polyvinyl chloride waste plastic handbag into a crusher for crushing to obtain polyvinyl chloride waste plastic powder;
(2) Weighing 10g of polyvinyl chloride waste plastic powder in a ball milling tank, adding 20mLN, N-dimethylformamide, adding stainless steel balls with the total mass of 100g, and then ball milling for 4 hours at a rotating speed of 500 rpm to obtain a mixed product;
(3) And (3) placing the porous carbon precursor obtained in the step (2) into a tubular furnace, purging and removing air in the tubular furnace at room temperature with the flow rate of nitrogen being 50mL/min under the nitrogen atmosphere, heating to 600 ℃ at the heating rate of 5 ℃/min, roasting for 2 hours, and naturally cooling to room temperature to obtain the polyvinyl chloride waste plastic derivative nano porous carbon material with almost no carbon output.
Application examples: the porous carbon materials obtained in examples 1 to 8 and comparative example 1 and commercially available activated carbon were used as catalysts in the reaction of preparing vinyl chloride from acetylene and hydrogen chloride: 2mL of each catalyst was taken to carry out acetylene hydrochlorination, and the acetylene and hydrogen chloride pressures were: 0.1MPa, n (C) 2 H 2 ) N (HCl) =1:1.2, and the space velocity of acetylene is controlled to be 60h -1 Before the reaction, nitrogen is used for purging and removing moisture and air in the system, then heating is started, acetylene and hydrogen chloride are simultaneously introduced for reaction when the temperature is raised to 220 ℃, the space-time yields of the vinyl chloride with the product of the example 1 and the activated carbon as catalysts at different times are recorded in the reaction process, and an activity evaluation chart is shown in figure 8; after 30h of reaction, the space-time yields and selectivity data for vinyl chloride with each catalyst are shown in Table 1.
TABLE 1 comparison of vinyl chloride space time yields and selectivities over different catalysts
From table 1, the main reasons for the difference of the catalytic performance of different carbon catalysts are that the defect structure and the nitrogen content are influenced together, and the excessively high nitrogen content can damage the pi electronic structure of the carbon material and the six-membered ring skeleton of the carbon material, so that the electronic structure around the carbon atoms can be damaged, and the adsorption capacity of the active center to acetylene is influenced, thereby reducing the hydrochlorination performance of the acetylene. As the doping amount of N exceeds a certain limit>20%), the defective structure of the material increases, and the skeleton structure of the carbon material breaks, which may be one of the reasons for affecting the catalytic performance thereof; meanwhile, a large amount of melamine molecules which are not crosslinked with halogen-containing plastics can be generated by adding excessive melamine, the pore structure of the carbon material can be blocked in the pyrolysis process, the specific surface area of the carbon material is reduced, and the catalytic performance of the carbon material is further influenced; taking example 3 as an example, the material has the highest nitrogen content of 29.9% and a specific surface area of only 37m due to the blocking of the pores of melamine 2 /g, resulting in minimal activity; the catalysts obtained in examples 2, 5 and 7 have lower yields of vinyl chloride than the catalyst obtained in example 1, mainly because the catalysts obtained in examples 2, 5 and 7 have much lower nitrogen content than the catalyst obtained in example 1, and thus have lower yields of vinyl chloride when used as catalysts for hydrochlorination of acetylene.
As can be clearly seen from FIG. 8, the yield of the vinyl chloride of the nano porous carbon material derived from the polyvinyl chloride waste plastics obtained by the invention is far higher than that of the activated carbon, and the catalytic performance of the nano porous carbon material is tens of times that of the activated carbon.
Claims (9)
1. The preparation method of the waste plastic derived nano porous carbon material is characterized by comprising the following steps:
1) Crushing waste plastics into powder, adding the powder, a solvent and melamine into a ball milling tank for grinding reaction to obtain a porous carbon precursor mixture, wherein the mass ratio of the waste plastics to the melamine is 1:0.5-1.5;
2) Washing the porous carbon precursor mixture obtained in the step 1) with deionized water, and drying to obtain a porous carbon precursor;
3) And 2) carrying out heat treatment on the porous carbon precursor obtained in the step 2) under the protection of inert atmosphere at a certain temperature, and naturally cooling to room temperature to obtain the waste plastic derivative nano porous carbon material.
2. The method for preparing the waste plastic-derived nano-porous carbon material according to claim 1, wherein the waste plastic is halogen-containing waste plastic, and specifically comprises polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, chlorinated rubber or chlorinated polypropylene.
3. The method for preparing a waste plastic-derived nanoporous carbon material according to claim 1, wherein the solvent in step 1) is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and cyclohexanone.
4. The method for preparing the waste plastic-derived nanoporous carbon material according to claim 1, wherein the grinding method in step 1) is manual grinding or ball milling; during ball milling, the ball ratio is 1: 5-15, the ball milling rotating speed is 400-600 rpm, and the ball milling time is 1-4 h.
5. The method for preparing a waste plastic-derived nanoporous carbon material according to claim 1, wherein the drying temperature in step 2) is 70 to 120 ℃ and the drying time is 8 to 12 hours.
6. The method for preparing the waste plastic-derived nanoporous carbon material according to claim 1, wherein the heat treatment process in step 3) is as follows: heating to 600-1000 ℃ at a heating rate of 5-10 ℃/min, roasting at constant temperature for 1-2 h for carbonization, and naturally cooling to room temperature after carbonization to obtain the waste plastic derivative nano porous carbon material.
7. The method for preparing the waste plastic-derived nanoporous carbon material according to claim 1, wherein the inert gas in the step 3) is nitrogen, argon or helium, and the flow rate of the inert gas is 30-100 mL/min.
8. A waste plastic-derived nanoporous carbon material produced according to the method of any one of claims 1 to 7.
9. The use of the waste plastic-derived nanoporous carbon material according to claim 8 as a carbon-based nonmetallic catalyst in the reaction of preparing vinyl chloride from acetylene hydrogen chloride.
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