CN110368971B - SiC-based composite catalyst for microwave-assisted depolymerization of solid waste and preparation method thereof - Google Patents
SiC-based composite catalyst for microwave-assisted depolymerization of solid waste and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000002910 solid waste Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 10
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- 239000005011 phenolic resin Substances 0.000 claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 6
- 239000007833 carbon precursor Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 103
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000008098 formaldehyde solution Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 239000012684 catalyst carrier precursor Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 5
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 4
- 229940115457 cetyldimethylethylammonium bromide Drugs 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910015221 MoCl5 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 3
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- 150000001805 chlorine compounds Chemical group 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims 1
- 230000033228 biological regulation Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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Abstract
The invention discloses a SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes and a preparation method thereof, wherein the SiC-based composite catalyst comprises a carrier, an active component and a cocatalyst component, the carrier is a SiC @ C core-shell composite material, and the SiC @ C core-shell composite material is prepared by growing a rectangular carbon nanotube on the surface of SiC by taking water-soluble phenolic resin synthesized by phenol and formaldehyde as a carbon precursor; the cocatalyst component is a transition metal oxide and is loaded in the rectangular hole of the carbon nanotube; the active component is a noble metal and is loaded in the rectangular hole of the carbon nanotube; and the mass ratio of the carrier, the cocatalyst component and the active component is 1 (0.005-0.01) to (0.01-0.05). The SiC-based composite catalyst prepared by the invention is used for the microwave-assisted depolymerization process of the solid waste, effectively improves the depolymerization degree and the depolymerization efficiency of the solid waste, simultaneously promotes the directional regulation and control of microwave-assisted depolymerization products, and greatly promotes the efficient high-valued utilization of the solid waste.
Description
Technical Field
The invention belongs to the field of catalytic conversion of waste resources, and particularly relates to a SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes and a preparation method thereof.
Background
The microwave is a radio frequency electromagnetic wave with wave-particle duality, the wavelength is about 1m to 1mm, the corresponding frequency is in the range of 0.3GHz to 300GHz, and the microwave is a general name of a decimetric wave, a centimeter wave and a millimeter wave. The property of the microwave is different from that of other electromagnetic waves, for example, the microwave has selectivity during microwave heating, small thermal inertia and strong penetrability, and the property of the microwave has certain similarity with geometric optics and sound waves, namely, has the characteristics of optical similarity and sound similarity, and the microwave also has the characteristics of nonionization, informativeness and the like. The microwave as a high-efficiency clean new energy can directly act with a chemical system to promote the chemical reaction, for example, the microwave can be used for organic and inorganic synthesis reaction, induced catalytic reaction, separation and extraction, preparation of nano particles, chemical synthesis and analysis of plasma, and the like. Compared with the traditional heating mode, the microwave heating has the advantages of high heating speed, low energy consumption, small loss and the like, the microwave heating is that the microwave rapidly permeates into the object at the light speed, the microwave acts on the polar medium material, the polar medium material is a wave-absorbing material, the electromagnetic energy can be converted into heat energy, almost no reflection exists, the energy is saved rapidly, and therefore, the microwave is widely applied to the depolymerization process of the biomass. The conventional depolymerization process is that heat energy is conducted from the surface of the raw material to the inside at a low heat transfer rate, so that free radicals with benzene rings are easily condensed into charcoal, and the sufficient depolymerization of biomass resources is not facilitated. The microwave-assisted depolymerization mode can integrally penetrate through an organic carbon bond structure by means of microwave dielectric heating, so that energy is rapidly transmitted to each functional group of a reactant to generate a non-pyrogenic effect, the reaction process is changed and the reaction activation energy is reduced by changing the isenthalpic or entropy effect of molecular arrangement, and the full conversion of biomass resources is facilitated.
Microwave-assisted depolymerization has obvious effects on accelerating the reaction rate and improving the yield of liquid products, but has weak selectivity on certain products, such as monophenol compounds, and especially has no obvious effect on directional breaking of carbon-carbon bonds with larger bond energy, so that the realization of directional shearing and conversion of main connecting bonds in a biomass resource structure by introducing a catalytic component is the key for obtaining a directional regulation product with high-efficiency conversion. The conventional metal catalyst has far lower wave-absorbing and heat-transferring efficiency than that of a polar medium material, and the microwave condition can inhibit active components of the catalyst and influence the catalytic conversion efficiency of the catalyst, so that the catalyst which can adapt to the microwave environment needs to be prepared, and the synergy of wave-absorbing and heat-transferring and catalytic conversion is realized. At present, solid wastes in nature and living production have large yield, large storage amount and large resource consumption and are harmful to the environment, and the solid wastes can be converted into new-form substances through microwave depolymerization, such as biological oil and chemicals with high added values, so that the high-efficiency high-value utilization of the solid wastes is realized.
Disclosure of Invention
The invention aims to provide a SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes and a preparation method thereof, aiming at overcoming the defects of the prior art. The catalyst is used for carrying out microwave-assisted catalytic depolymerization on the solid waste and realizing directional regulation and control of products, thereby realizing high-efficiency and high-value utilization of the solid waste.
In order to achieve the purpose, the invention adopts the following technical scheme:
a SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes comprises a carrier, an active component and a cocatalyst component, wherein the carrier is a SiC @ C core-shell composite material, and the SiC @ C core-shell composite material is prepared by growing a rectangular carbon nanotube on the surface of SiC by using a water-soluble phenolic resin synthesized from phenol and formaldehyde as a carbon precursor; the cocatalyst component is a transition metal oxide and is loaded in the rectangular hole of the carbon nanotube; the active component is a noble metal and is loaded in the rectangular hole of the carbon nanotube; and the mass ratio of the carrier, the cocatalyst component and the active component is 1 (0.005-0.01) to (0.01-0.05).
Further, the SiC is a microwave absorption medium, the particle size is 50 nm-0.5 mm, the length of the rectangular carbon nanotube is 0.5-10 mu m, the long side of the tube hole is 50-100 nm, and the short side of the tube hole is 10-100 nm.
Further, the transition metal oxide is NiO, ZnO and TiO2、CuO、Fe2O3、MoO3And CoO.
Further, the noble metal is one of Pd, Pt, Ru, Rh, Ag and Au.
A preparation method of a SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes comprises the following steps:
the method comprises the following steps: putting SiC into a reaction container, adding 0.01mol/L surfactant solution, and carrying out ultrasonic treatment for 20min at the ultrasonic frequency of 30-50 kHz to form suspension, wherein the mass ratio of the surfactant solution to the SiC is (8-12) to 1;
step two: adding phenol into the suspension obtained in the first step, sequentially adding a NaOH solution with the mass fraction of 30% and a formaldehyde solution with the mass fraction of 37%, stirring and heating, uniformly heating the temperature of the reaction solution to 90-100 ℃ within 40-50 min, and then preserving the temperature for 10-30 min, wherein the mass ratio of phenol to SiC is (0.2-3): 1, the mass ratio of the NaOH solution to phenol is (0.5-1): 1, and the mass ratio of the formaldehyde solution to phenol is (0.5-3): 1;
step three: after the second step is finished, reducing the temperature of the reaction system to 80 ℃, adding a NaOH solution with the mass fraction of 30% and a formaldehyde solution with the mass fraction of 37% for the second time, then raising the temperature of the reaction solution to 90-100 ℃, preserving the temperature for 30-50 min, immediately cooling, and discharging when the temperature of the reaction solution is reduced to below 40 ℃, wherein the mass ratio of the NaOH solution to the phenol is (0.1-0.3): 1, and the mass ratio of the formaldehyde solution to the phenol is (0.1-1): 1;
step four: washing the product obtained in the third step with ethanol and deionized water, and then drying to obtain a SiC @ PF catalyst carrier precursor;
step five: adding a precursor of a SiC @ PF catalyst carrier into N2Calcining in a steam atmosphere to obtain the SiC @ C catalyst carrier, wherein the calcining condition is that after the temperature is raised to 700-900 ℃ at the temperature raising rate of 1-5 ℃/min, the temperature is kept for 4-6 h;
step six: adding the SiC @ C catalyst carrier into a chloride solution of a cocatalyst component, stirring uniformly at room temperature, carrying out ultrasonic treatment for 5-10 min at an ultrasonic frequency of 40-60 kHz, then adding a salt solution of an active component, stirring uniformly at room temperature, carrying out ultrasonic impregnation for 30-60 min at an ultrasonic frequency of 40-60 kHz, and then carrying out sealed impregnation for 24-48 h at room temperature; the chloride solution of the cocatalyst component is a chloride solution of a transition metal oxide, the concentration of the chloride solution is 1 wt%, the salt solution of the active component is a salt solution of a noble metal, the concentration of the salt solution is 2 wt%, and the mass ratio of the carrier, the cocatalyst component and the active component is 1 (0.005-0.01) to 0.01-0.05;
step seven: drying the product obtained in the sixth step, and then adding the dried product into N2And (3) heating to 500-800 ℃ under the action of 50-300W microwaves in the atmosphere, and preserving the temperature for 1-4 hours to obtain the SiC-based composite catalyst.
Further, in the first step, the surfactant is one of cetyl trimethyl ammonium bromide, cetyl dimethyl ethyl ammonium bromide, cetyl trimethyl ammonium chloride and dodecyl trimethyl ammonium bromide.
Further, the drying mode in the fourth step and the seventh step is vacuum freeze drying or spray drying.
Further, N corresponding to the precursor of the SiC @ PF catalyst carrier per gram in the fifth step2The flow rate is 10-100 mL/min, and the flow rate of water vapor is 0.01-0.5 mL/min.
Further, the chloride solution of the cocatalyst component is NiCl2Solution, ZnCl2Solution, CuCl2Solution, FeCl3Solution, MoCl5Solution, CoCl2Solution and TiCl4One of the solutions.
Further, the salt solution of the active component is H2PtCl6Solution, HAuCl4Solution, AgNO3Solution, PdCl2Solutions, RhCl3Solution and RuCl3One of the solutions.
Compared with the prior art, the invention has the following beneficial technical effects:
1. according to the invention, on the traditional microwave absorbing medium SiC, the carbon nano tube is grown on the SiC surface by a simple phenolic resin (PF) synthesis method, so that the specific surface area and the load performance of SiC are greatly improved, and an effective way is provided for taking SiC as a catalyst carrier.
2. According to the invention, the inorganic wave-absorbing heat-transfer material SiC and the organic carbon material phenolic resin (PF) are combined by a cationic surfactant and a surface static stabilization mechanism, so that the stable combination of the inorganic material and the organic material is realized, the new surface characteristics of the inorganic material SiC are endowed, and the formation of the rectangular carbon nanotube is realized by combining the carbonization condition (the temperature is raised to 700-900 ℃ at 1-5 ℃/min and is kept for 4-6 h).
3. The invention designs and synthesizes the SiC-based composite catalyst which is suitable for a microwave-assisted catalytic depolymerization system by using a commercially mature microwave absorbing medium SiC as a core, enhances the wave absorbing performance of the catalyst by utilizing the interaction of SiC and C interfaces, improves the loading effect of metal active components by controlling the appearance of shell carbon (C), and realizes the unification of double functions of wave absorbing, strengthening and heat transfer and catalytic high-efficiency depolymerization.
4. According to the invention, the SiC-based composite catalyst is obtained by heating to 500-800 ℃ under the action of 50-300W microwaves and preserving heat for 1-4 h, the heating reduction is realized by utilizing the characteristic that SiC absorbs the microwaves, the effective load of the active component and the auxiliary catalytic component of the catalyst is realized, and the obtained catalyst has high activity strength and is easy to recycle.
5. The SiC-based composite catalyst prepared by the invention is used for the microwave-assisted depolymerization process of the solid waste, effectively improves the depolymerization degree and the depolymerization efficiency of the solid waste, simultaneously promotes the directional regulation and control of microwave-assisted depolymerization products, and greatly promotes the efficient high-valued utilization of the solid waste.
Drawings
FIG. 1 is an SEM image of the SiC @ C catalyst support of example 1.
Detailed Description
Embodiments of the invention are described in further detail below:
the SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes provided by the invention comprises a carrier, an active component and a cocatalyst component. The carrier is a SiC @ C core-shell composite material, and specifically, a water-soluble phenolic resin synthesized from phenol and formaldehyde is used as a carbon precursor, and a rectangular carbon nano tube grows on the surface of SiC. The SiC is a microwave absorption medium, the particle size is 50 nm-0.5 mm, the length of the rectangular carbon nanotube is 0.5-10 mu m, the long side of the tube hole is 50-100 nm, and the short side of the tube hole is 10-100 nm. The catalyst promoter component is transition metal oxide and is loaded in the rectangular holes of the carbon nano tubes. The active component is noble metal and is loaded in the rectangular hole of the carbon nano tube. The transition metal oxide is NiO, ZnO or TiO2、CuO、Fe2O3、MoO3And CoO, wherein the noble metal is any one of Pd, Pt, Ru, Rh, Ag and Au. The mass ratio of the carrier to the cocatalyst component to the active component is 1 (0.005-0.01) to (0.01-0.05).
The invention provides a preparation method of a SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes, which comprises the following steps:
(1) and (3) placing the SiC in a reaction container, adding 0.01mol/L of surfactant solution, and carrying out ultrasonic treatment for 20min at the ultrasonic frequency of 30-50 kHz to form suspension. The mass ratio of the 0.01mol/L surfactant solution to SiC is (8-12): 1. The surfactant is any one of Cetyl Trimethyl Ammonium Bromide (CTAB), cetyl dimethyl ethyl ammonium bromide (CDAB), Cetyl Trimethyl Ammonium Chloride (CTAC) and Dodecyl Trimethyl Ammonium Bromide (DTAB).
(2) Adding phenol into the suspension obtained in the step (1), sequentially adding a NaOH solution with the mass fraction of 30% and a formaldehyde solution with the mass fraction of 37%, stirring and heating, uniformly heating the reaction solution to 90-100 ℃ within 40-50 min, and then preserving the temperature for 10-30 min. The mass ratio of phenol to SiC is (0.2-3): 1, the mass ratio of 30% NaOH solution to phenol is (0.5-1): 1, and the mass ratio of formaldehyde (37%) to phenol is (0.5-3): 1.
(3) After the step (2) is finished, reducing the temperature of the reaction system to 80 ℃, adding a NaOH solution with the mass fraction of 30% and a formaldehyde solution with the mass fraction of 37% for the second time, then raising the temperature of the reaction system to 90-100 ℃, preserving the temperature for 30-50 min, immediately cooling, and discharging when the internal temperature is reduced to below 40 ℃. The mass ratio of the 30% NaOH solution to the phenol is (0.1-0.3): 1, and the mass ratio of the formaldehyde (37%) to the phenol is (0.1-1): 1.
(4) And (4) washing the product obtained in the step (3) with ethanol for 1 time, washing with deionized water for 1-4 times, and drying to obtain the SiC @ PF catalyst carrier precursor. The drying mode is one of vacuum freeze drying and spray drying.
(5) Adding a precursor of a SiC @ PF catalyst carrier into N2And calcining in a steam atmosphere to obtain the SiC @ C catalyst carrier. N corresponding to precursor of SiC @ PF catalyst carrier per gram2The flow rate is 10-100 mL/min, and the flow rate of the water vapor is 0.01-0.5 mL/min; the calcining condition is that the temperature is raised to 700-900 ℃ at the speed of 1-5 ℃/min, and the temperature is kept for 4-6 h.
(6) Adding the SiC @ C catalyst carrier into a chloride solution of a cocatalyst component, stirring for 10min at room temperature, carrying out ultrasonic treatment for 5-10 min at an ultrasonic frequency of 40-60 kHz, then adding a salt solution of an active component, stirring for 20-40 min at room temperature, carrying out ultrasonic impregnation for 30-60 min at an ultrasonic frequency of 40-60 kHz, and then carrying out sealed impregnation for 24-48 h at room temperature. The chloride solution of the cocatalyst component is NiCl2、ZnCl2、CuCl2、FeCl3、MoCl5、CoCl2、TiCl4One of the solutions, with a concentration of 1 wt%, the salt solution of the active ingredient is H2PtCl6、HAuCl4、AgNO3、PdCl2、RhCl3、RuCl3Of 2 wt% concentration. The mass ratio of the carrier to the cocatalyst component to the active component is 1 (0.005-0.01) to (0.01-0.05).
(7) Drying the product obtained in the step (6), and then adding the dried product into N2And (3) heating to 500-800 ℃ under the action of 50-300W microwaves in the atmosphere, and preserving heat for 1-4 hours to obtain the SiC-based composite catalyst, wherein the drying mode is one of vacuum freeze drying and spray drying.
The present invention is described in further detail below with reference to examples:
example 1
1g of SiC was placed in a reaction vessel, and 8g of a 0.01mol/L cetyltrimethylammonium bromide solution was added thereto, and ultrasonic treatment was carried out at an ultrasonic frequency of 30kHz for 20 minutes to form a suspension. Then 0.2g of phenol is added, 0.1g of NaOH solution with the mass fraction of 30% and 0.1g of formaldehyde solution with the mass fraction of 37% are sequentially added, then stirring and heating are started, the temperature of the reaction solution is uniformly increased to 90 ℃ within 40min, and then the temperature is kept for 30 min. And then reducing the temperature of the reaction system to 80 ℃, adding 0.02g of NaOH solution with the mass fraction of 30% and 0.02g of formaldehyde with the mass fraction of 37% for the second time, then raising the temperature of the reaction system to 90 ℃, preserving the temperature for 50min, immediately reducing the temperature, and discharging when the internal temperature is reduced to below 40 ℃. And washing the obtained product with ethanol for 1 time, washing the product with deionized water for 1 time, and then performing vacuum freeze drying to obtain the SiC @ PF catalyst carrier precursor. Taking 1g of the obtained SiC @ PF catalyst carrier precursor, adding into N2And calcining in a steam atmosphere, N2The flow is 10mL/min, the water vapor flow is 0.01mL/min, the temperature is raised to 700 ℃ at the speed of 1 ℃/min, and then the temperature is kept for 6h to obtain the SiC @ C catalyst carrier, wherein the figure 1 is an SEM image of the SiC @ C catalyst carrier, and a large number of rectangular carbon nanotubes can be obviously seen growing on the surface of SiC. Adding the SiC @ C catalyst carrier to NiCl with the concentration of 1 wt%2Stirring the solution at room temperature for 10min at 40kHz ultrasonic frequencyUltrasonic treating for 10min, and adding 2 wt% H2PtCl6Stirring the solution at room temperature for 20min, ultrasonic soaking at ultrasonic frequency of 40kHz for 60min, and sealing and soaking at room temperature for 48 h. The product was freeze dried under vacuum and then placed under N2And (3) raising the temperature to 500 ℃ in the atmosphere under the action of 50W microwaves, and preserving the temperature for 4 hours to obtain the Pt-NiO/SiC-based composite catalyst. XPS characterization of the catalyst shows that the content of Pt as an active component on the catalyst is 4.25%, and the content of NiO as an auxiliary catalyst component is 0.48%. The obtained Pt-NiO/SiC-based composite catalyst is used for a microwave-assisted depolymerization experiment of corn straw particles, and reacts at a reaction temperature of 600 ℃ for 30min under a microwave power of 1000W, so that the yield of liquid products converted from corn straws is 40.2%.
Example 2
1g of SiC was placed in a reaction vessel, 10g of a 0.01mol/L hexadecyldimethylethyl ammonium bromide solution was added, and ultrasonic treatment was carried out at an ultrasonic frequency of 35kHz for 20 minutes to form a suspension. Then 2g of phenol is added, 0.7g of NaOH solution with the mass fraction of 30% and 1.5g of formaldehyde solution with the mass fraction of 37% are sequentially added, then stirring and heating are started, the temperature of the reaction solution is uniformly increased to 95 ℃ within 45min, and then the temperature is kept for 15 min. And then, reducing the temperature of the reaction system to 80 ℃, adding 0.2g of NaOH solution with the mass fraction of 30% and 0.4g of formaldehyde solution with the mass fraction of 37% for the second time, then raising the temperature of the reaction solution to 95 ℃, preserving the temperature for 35min, immediately reducing the temperature, and discharging when the temperature of the reaction solution is reduced to below 40 ℃. And washing the obtained product with ethanol for 1 time, washing with deionized water for 2 times, and then performing spray drying to obtain the SiC @ PF catalyst carrier precursor. Taking 1g of the obtained SiC @ PF catalyst carrier precursor, adding into N2And calcining in a steam atmosphere, N2The flow is 40mL/min, the flow of water vapor is 0.2mL/min, the temperature is raised to 900 ℃ at the speed of 2 ℃/min, and then the temperature is kept for 5h, so that the SiC @ C catalyst carrier is obtained. Adding a SiC @ C catalyst support to ZnCl at a concentration of 1 wt%2Stirring the solution at room temperature for 10min, performing ultrasonic treatment at 50kHz ultrasonic frequency for 8min, and adding 2 wt% HAuCl4Stirring the solution at room temperature for 25min, ultrasonic soaking at 50kHz ultrasonic frequency for 40min, and then maintaining the room temperatureAnd sealing and soaking for 32h at the temperature. The product was spray dried and then washed with N2Raising the temperature to 600 ℃ under the action of 150W microwave in the atmosphere, and preserving the temperature for 2h to obtain the Au-ZnO/SiC-based composite catalyst. XPS characterization of the catalyst shows that the catalyst has an active component Au content of 4.46% and a promoter component ZnO content of 0.57%. The obtained Au-ZnO/SiC-based composite catalyst is used for a microwave-assisted depolymerization experiment of the solid waste of the paper-making sludge, and reacts for 30min at a reaction temperature of 600 ℃ under the microwave power of 1000W, so that the yield of the liquid product converted from the solid waste of the paper-making sludge is 35.6%.
Example 3
1g of SiC was placed in a reaction vessel, 11g of a 0.01mol/L cetyltrimethylammonium chloride solution was added, and ultrasonic treatment was carried out at an ultrasonic frequency of 45kHz for 20 minutes to form a suspension. Then 4g of phenol is added, 1.8g of NaOH solution with the mass fraction of 30% and 5g of formaldehyde solution with the mass fraction of 37% are sequentially added, then stirring and heating are started, the temperature of the reaction solution is uniformly increased to 95 ℃ within 45min, and then the temperature is kept for 25 min. And then cooling the reaction system to 80 ℃, adding 0.5g of NaOH solution with the mass fraction of 30% and 1.4g of formaldehyde solution with the mass fraction of 37% for the second time, then heating the temperature of the reaction system to 95 ℃, preserving the temperature for 45min, immediately cooling, and discharging when the internal temperature is reduced to below 40 ℃. And washing the obtained product with ethanol for 1 time, washing with deionized water for 3 times, and then carrying out vacuum freeze drying to obtain the SiC @ PF catalyst carrier precursor. Taking 1g of the obtained SiC @ PF catalyst carrier precursor, adding into N2And calcining in a steam atmosphere, N2The flow is 70mL/min, the flow of water vapor is 0.4mL/min, the temperature is raised to 750 ℃ at the speed of 4 ℃/min, and then the temperature is preserved for 5.5h, so that the SiC @ C catalyst carrier is obtained. Adding a SiC @ C catalyst support to 1 wt% CuCl2Stirring the solution at room temperature for 10min, performing ultrasonic treatment at 55kHz ultrasonic frequency for 8min, and adding AgNO with concentration of 2 wt%3Stirring the solution at room temperature for 35min, ultrasonically soaking at 55kHz ultrasonic frequency for 50min, and sealing and soaking at room temperature for 40 h. The product was spray dried and then washed with N2Raising the temperature to 700 ℃ under the action of 250W microwave in the atmosphere, and preserving the temperature for 3 hours to obtain Ag-CuO/SiC-based composite materialA catalyst. XPS characterization of the catalyst shows that the catalyst has an active component Ag content of 4.69% and a cocatalyst CuO content of 0.78%. The obtained Ag-CuO/SiC-based composite catalyst is used for a microwave-assisted depolymerization experiment of pine sawdust, and reacts for 30min at a reaction temperature of 600 ℃ under a microwave power of 1000W, so that the yield of the pine sawdust converted into a liquid product is 58.7%.
Example 4
1g of SiC was placed in a reaction vessel, 12g of a 0.01mol/L dodecyltrimethylammonium bromide solution was added, and ultrasonic treatment was carried out at an ultrasonic frequency of 50kHz for 20 minutes to form a suspension. Then 5g of phenol is added, 3g of NaOH solution with the mass fraction of 30% and 9g of formaldehyde solution with the mass fraction of 37% are sequentially added, then stirring and heating are started, the temperature of the reaction solution is uniformly increased to 100 ℃ within 50min, and then the temperature is kept for 10 min. And then, reducing the temperature of the reaction system to 80 ℃, adding 30 mass percent NaOH solution and 37 mass percent formaldehyde solution 3g for the second time, then raising the temperature of the reaction system to 100 ℃, preserving the temperature for 30min, immediately reducing the temperature, and discharging when the internal temperature is reduced to below 40 ℃. And washing the obtained product with ethanol for 1 time, washing with deionized water for 4 times, and then carrying out vacuum freeze drying to obtain the SiC @ PF catalyst carrier precursor. Taking 1g of the obtained SiC @ PF catalyst carrier precursor, adding into N2And calcining in a steam atmosphere, N2The flow is 100mL/min, the flow of water vapor is 0.5mL/min, the temperature is raised to 800 ℃ at the speed of 5 ℃/min, and then the temperature is kept for 4h, so that the SiC @ C catalyst carrier is obtained. Adding a SiC @ C catalyst carrier to FeCl with a concentration of 1 wt%3Stirring the solution at room temperature for 10min, performing ultrasonic treatment at ultrasonic frequency of 60kHz for 5min, and adding PdCl with concentration of 2 wt%2Stirring the solution at room temperature for 40min, ultrasonically soaking at 60kHz ultrasonic frequency for 30min, and sealing and soaking at room temperature for 24 h. The product was freeze dried under vacuum and then placed under N2Raising the temperature to 800 ℃ under the action of 300W microwaves in the atmosphere, and preserving the temperature for 1h to obtain Pd-Fe2O3a/SiC-based composite catalyst. XPS characterization of the catalyst shows that the catalyst has an active component Pd content of 4.92% and a cocatalyst component Fe2O3The content is 0.94%. The obtained Pd-Fe2O3the/SiC-based composite catalyst is used for a microwave-assisted depolymerization experiment of waste plastic particle solid waste, and reacts for 30min at a reaction temperature of 600 ℃ under the microwave power of 1000W, so that the yield of the liquid product converted from the waste plastic particle solid waste is 53.8%.
Claims (10)
1. The SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes is characterized by comprising a carrier, an active component and a cocatalyst component, wherein the carrier is a SiC @ C core-shell composite material, and the SiC @ C core-shell composite material is formed by growing a rectangular carbon nanotube on the surface of SiC by taking water-soluble phenolic resin synthesized from phenol and formaldehyde as a carbon precursor; the cocatalyst component is a transition metal oxide and is loaded in the rectangular hole of the carbon nanotube; the active component is a noble metal and is loaded in the rectangular hole of the carbon nanotube; the mass ratio of the carrier, the cocatalyst component and the active component is 1 (0.005-0.01) to 0.01-0.05; the preparation method comprises the following steps:
the method comprises the following steps: putting SiC into a reaction container, adding 0.01mol/L surfactant solution, and carrying out ultrasonic treatment for 20min at the ultrasonic frequency of 30-50 kHz to form suspension, wherein the mass ratio of the surfactant solution to the SiC is (8-12) to 1;
step two: adding phenol into the suspension obtained in the first step, sequentially adding a NaOH solution with the mass fraction of 30% and a formaldehyde solution with the mass fraction of 37%, stirring and heating, uniformly heating the temperature of the reaction solution to 90-100 ℃ within 40-50 min, and then preserving the temperature for 10-30 min, wherein the mass ratio of phenol to SiC is (0.2-3): 1, the mass ratio of the NaOH solution to phenol is (0.5-1): 1, and the mass ratio of the formaldehyde solution to phenol is (0.5-3): 1;
step three: after the second step is finished, reducing the temperature of the reaction system to 80 ℃, adding a NaOH solution with the mass fraction of 30% and a formaldehyde solution with the mass fraction of 37% for the second time, then raising the temperature of the reaction solution to 90-100 ℃, preserving the temperature for 30-50 min, immediately cooling, and discharging when the temperature of the reaction solution is reduced to below 40 ℃, wherein the mass ratio of the NaOH solution to the phenol is (0.1-0.3): 1, and the mass ratio of the formaldehyde solution to the phenol is (0.1-1): 1;
step four: washing the product obtained in the third step with ethanol and deionized water, and then drying to obtain a SiC @ PF catalyst carrier precursor;
step five: adding a precursor of a SiC @ PF catalyst carrier into N2Calcining in a steam atmosphere to obtain the SiC @ C catalyst carrier, wherein the calcining condition is that after the temperature is raised to 700-900 ℃ at the temperature raising rate of 1-5 ℃/min, the temperature is kept for 4-6 h;
step six: adding the SiC @ C catalyst carrier into a chloride solution of a cocatalyst component, stirring uniformly at room temperature, carrying out ultrasonic treatment for 5-10 min at an ultrasonic frequency of 40-60 kHz, then adding a salt solution of an active component, stirring uniformly at room temperature, carrying out ultrasonic impregnation for 30-60 min at an ultrasonic frequency of 40-60 kHz, and then carrying out sealed impregnation for 24-48 h at room temperature; the chloride solution of the cocatalyst component is a chloride solution of a transition metal oxide, the concentration of the chloride solution is 1 wt%, the salt solution of the active component is a salt solution of a noble metal, the concentration of the salt solution is 2 wt%, and the mass ratio of the carrier, the cocatalyst component and the active component is 1 (0.005-0.01) to 0.01-0.05;
step seven: drying the product obtained in the sixth step, and then adding the dried product into N2And (3) heating to 500-800 ℃ under the action of 50-300W microwaves in the atmosphere, and preserving the temperature for 1-4 hours to obtain the SiC-based composite catalyst.
2. The SiC-based composite catalyst for microwave-assisted depolymerization of solid waste according to claim 1, wherein SiC is a microwave absorbing medium, the particle size is 50nm to 0.5mm, the length of the rectangular carbon nanotube is 0.5 to 10 μm, the long side of the tube hole is 50 to 100nm, and the short side is 10 to 100 nm.
3. The SiC-based composite catalyst for microwave-assisted depolymerization of solid waste according to claim 1, wherein said transition metal oxide is NiO, ZnO or TiO2、CuO、Fe2O3、MoO3And CoO.
4. The SiC-based composite catalyst for microwave-assisted depolymerization of solid waste according to claim 1, wherein the noble metal is one of Pd, Pt, Ru, Rh, Ag and Au.
5. A preparation method of a SiC-based composite catalyst for microwave-assisted depolymerization of solid wastes is characterized by comprising the following steps:
the method comprises the following steps: putting SiC into a reaction container, adding 0.01mol/L surfactant solution, and carrying out ultrasonic treatment for 20min at the ultrasonic frequency of 30-50 kHz to form suspension, wherein the mass ratio of the surfactant solution to the SiC is (8-12) to 1;
step two: adding phenol into the suspension obtained in the first step, sequentially adding a NaOH solution with the mass fraction of 30% and a formaldehyde solution with the mass fraction of 37%, stirring and heating, uniformly heating the temperature of the reaction solution to 90-100 ℃ within 40-50 min, and then preserving the temperature for 10-30 min, wherein the mass ratio of phenol to SiC is (0.2-3): 1, the mass ratio of the NaOH solution to phenol is (0.5-1): 1, and the mass ratio of the formaldehyde solution to phenol is (0.5-3): 1;
step three: after the second step is finished, reducing the temperature of the reaction system to 80 ℃, adding a NaOH solution with the mass fraction of 30% and a formaldehyde solution with the mass fraction of 37% for the second time, then raising the temperature of the reaction solution to 90-100 ℃, preserving the temperature for 30-50 min, immediately cooling, and discharging when the temperature of the reaction solution is reduced to below 40 ℃, wherein the mass ratio of the NaOH solution to the phenol is (0.1-0.3): 1, and the mass ratio of the formaldehyde solution to the phenol is (0.1-1): 1;
step four: washing the product obtained in the third step with ethanol and deionized water, and then drying to obtain a SiC @ PF catalyst carrier precursor;
step five: adding a precursor of a SiC @ PF catalyst carrier into N2Calcining in a steam atmosphere to obtain the SiC @ C catalyst carrier, wherein the calcining condition is that after the temperature is raised to 700-900 ℃ at the temperature raising rate of 1-5 ℃/min, the temperature is kept for 4-6 h;
step six: adding the SiC @ C catalyst carrier into a chloride solution of a cocatalyst component, stirring uniformly at room temperature, carrying out ultrasonic treatment for 5-10 min at an ultrasonic frequency of 40-60 kHz, then adding a salt solution of an active component, stirring uniformly at room temperature, carrying out ultrasonic impregnation for 30-60 min at an ultrasonic frequency of 40-60 kHz, and then carrying out sealed impregnation for 24-48 h at room temperature; the chloride solution of the cocatalyst component is a chloride solution of a transition metal oxide, the concentration of the chloride solution is 1 wt%, the salt solution of the active component is a salt solution of a noble metal, the concentration of the salt solution is 2 wt%, and the mass ratio of the carrier, the cocatalyst component and the active component is 1 (0.005-0.01) to 0.01-0.05;
step seven: drying the product obtained in the sixth step, and then adding the dried product into N2And (3) heating to 500-800 ℃ under the action of 50-300W microwaves in the atmosphere, and preserving the temperature for 1-4 hours to obtain the SiC-based composite catalyst.
6. The method for preparing the SiC-based composite catalyst for microwave-assisted depolymerization of solid waste according to claim 5, wherein the surfactant in the first step is one of cetyltrimethylammonium bromide, cetyldimethylethylammonium bromide, cetyltrimethylammonium chloride and dodecyltrimethylammonium bromide.
7. The method for preparing the SiC-based composite catalyst for microwave-assisted depolymerization of solid waste according to claim 5, wherein the drying manner in the fourth and seventh steps is vacuum freeze drying or spray drying.
8. The preparation method of the SiC-based composite catalyst for microwave-assisted depolymerization of solid waste according to claim 5, wherein N corresponding to per gram of SiC @ PF catalyst carrier precursor in the fifth step2The flow rate is 10-100 mL/min, and the flow rate of water vapor is 0.01-0.5 mL/min.
9. The method for preparing the SiC-based composite catalyst for microwave-assisted depolymerization of solid waste according to claim 5, wherein the chloride solution of the co-catalyst component is NiCl2Solution, ZnCl2Solution, CuCl2Solution, FeCl3Solution, MoCl5Solution, CoCl2Solution and TiCl4One of the solutions.
10. The method for preparing the SiC-based composite catalyst for microwave-assisted depolymerization of solid waste according to claim 5, wherein the salt solution of the active component is H2PtCl6Solution, HAuCl4Solution, AgNO3Solution, PdCl2Solutions, RhCl3Solution and RuCl3One of the solutions.
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