CN109261196B - Preparation method of high-dielectric composite microporous molecular sieve catalyst - Google Patents
Preparation method of high-dielectric composite microporous molecular sieve catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims abstract description 47
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 7
- 238000000120 microwave digestion Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 238000000197 pyrolysis Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000001833 catalytic reforming Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000000295 fuel oil Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000003760 tallow Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- 239000002028 Biomass Substances 0.000 abstract description 7
- 238000007233 catalytic pyrolysis Methods 0.000 abstract description 6
- 239000010802 sludge Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000008157 edible vegetable oil Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- 239000006260 foam Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000012075 bio-oil Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- Toxicology (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
A preparation method of a high dielectric composite microporous molecular sieve catalyst comprises the steps of calcining silicon carbide foamed ceramic; then, uniformly mixing tetrapropylammonium hydroxide, tetraethyl orthosilicate, sodium chloride, sodium aluminate and water, stirring, standing and forming gel; mixing the silicon carbide foamed ceramic with the gel, loading the mixture into a reaction kettle, placing the reaction kettle into a microwave digestion instrument, and carrying out microwave treatment; and then cleaning, transferring to a muffle furnace for calcining, then placing in an ammonium chloride solution, and finally calcining in the muffle furnace to obtain the high-dielectric composite microporous molecular sieve catalyst. The addition of the high-dielectric composite microporous molecular sieve catalyst changes the temperature rise and the catalytic behavior of the traditional catalyst in a reaction system, and effectively improves the catalytic efficiency of the catalyst. Can be widely applied to microwave-assisted catalytic pyrolysis of biomass, non-edible oil and sludge.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a preparation method and application of a high-dielectric composite microporous molecular sieve catalyst.
Background
The selection of the catalyst in the biomass microwave rapid catalytic pyrolysis method is very important. In recent years, microporous, mesoporous and macroporous catalysts (ZSM-5, MCM-41, FCC, LOSA-1, SBA-15, CNT and modified derivatives of the catalysts) are widely applied to catalytic pyrolysis reaction, and research results show that microporous molecular sieves and mesoporous molecular sieves have good catalytic pyrolysis effects. Wherein, the ZSM-5 molecular sieve is the most widely and effectively used catalyst at present, has good catalytic deoxidation effect, can lead the oxygen-containing substances in the primary pyrolysis steam to be catalytically cracked to form hydrocarbons, and the O is H2O、CO、CO2Is removed in the form of (1). The ZSM-5 molecular sieve has straight pore channels and chord typeThe oxygen-containing substances in the primary pyrolysis steam are catalytically deoxidized in the pore channels through reactions such as dehydration, decarbonylation, decarboxylation and the like.
Although microporous molecular sieves are widely applied and have good effects in microwave rapid catalytic pyrolysis of biomass, a series of outstanding problems still exist at the same time, including: (1) the microporous molecular sieve catalyst is easy to coke and deactivate, the service life is influenced, the generation of coke mainly refers to the further polymerization of pyrolysis products on the surface of the molecular sieve catalyst, the formation process is a series of shape-selective reactions of deep dehydrogenation, and the coke mainly comprises macromolecular condensed ring aromatic hydrocarbon substances with more carbon and less hydrogen. As for the HZSM-5 catalyst, the sizes of two pore channels are small, so that the inner surface of the HZSM-5 catalyst does not have a coke growth extension space, and coke with a large molecular structure can only be generated on the outer surface of the HZSM-5 catalyst. The formation of coke can cause the plugging of catalyst channels, limiting the diffusion of reactants into the catalyst channels, and causing the catalyst to lose catalytic activity. (2) The aperture radius of the microporous molecular sieve is small, and macromolecular substances are difficult to effectively enter, so that the microporous molecular sieve is suitable for catalytic deoxidation of the small molecular substances, and the pyrolysis oil is rich in macromolecular substances and easy to age. If the pyrolysis steam can be quickly catalyzed and pyrolyzed into small molecules before entering the microporous molecular sieve, the bio-oil can be effectively upgraded.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-dielectric composite microporous molecular sieve catalyst.
The invention is realized by the following technical scheme.
The preparation method of the high-dielectric composite microporous molecular sieve catalyst comprises the following steps.
(1) The silicon carbide foamed ceramic is placed in a muffle furnace to be calcined for 3-6h at the temperature of 850-1000 ℃.
(2) The following substances in parts by mass: 20-30 parts of 2 mol/L tetrapropylammonium hydroxide solution, 60-70 parts of tetraethyl orthosilicate, 10-15 parts of sodium chloride, 0.4-0.8 part of sodium aluminate and 1100 parts of water 900-containing sodium sulfonate, uniformly mixing, stirring strongly for 3-5 h, and standing for 10-20min to form gel.
(3) Mixing the silicon carbide foam ceramic calcined in the step (1) with the gel in the step (2) according to the mass ratio of 1:2-1:1, putting the mixture into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle in a microwave digestion instrument, performing microwave power of 600-.
(4) And (3) cleaning the silicon carbide foamed ceramic reacted in the step (3) with distilled water for 3-5 times, transferring to a muffle furnace, calcining at 650 ℃ for 5-7 h, then placing in 1mol/L ammonium chloride solution at 75-90 ℃ for 20-36h, and transferring to the muffle furnace, calcining at 600 ℃ for 3-5 h to obtain the high-dielectric composite microporous molecular sieve catalyst.
When biomass pyrolysis steam passes through the high-dielectric composite microporous molecular sieve catalyst, the biomass pyrolysis steam firstly enters external high-dielectric porous ceramic, the external high-dielectric porous ceramic quickly absorbs microwaves in a microwave field to raise the temperature so as to catalytically pyrolyze macromolecular substances into small molecular substances in a microwave-assisted manner, and then all the small molecular substances enter the internal microporous molecular sieve to realize efficient deoxidation, so that the obtained bio-oil is rich in hydrocarbons and is not easy to age. The invention has very important theoretical and practical significance for improving the comprehensive utilization level of biomass and relieving the energy shortage in China.
The addition of the high-dielectric composite microporous molecular sieve catalyst changes the temperature rise and the catalytic behavior of the traditional catalyst in a reaction system, and effectively improves the catalytic efficiency of the catalyst. Can be widely applied to microwave-assisted catalytic pyrolysis of biomass, non-edible oil and sludge.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1.
The silicon carbide ceramic foam was calcined in a muffle furnace at 900 ℃ for 4 h. Then accurately weighing 25 g of 2 mol/L tetrapropyl ammonium hydroxide solution, 65 g of tetraethyl orthosilicate, 12 g of sodium chloride, 0.5 g of sodium aluminate and 1000 g of water, stirring strongly for 4 hours, and standing for 15 min to form gel; mixing the calcined silicon carbide foamed ceramic with gel according to the mass ratio of 1:2, putting the mixture into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into a microwave digestion instrument, controlling the microwave power to be 800W, controlling the temperature to be 160 ℃, and reacting for 3 hours; and washing the reacted silicon carbide foamed ceramic with distilled water for 5 times, transferring the silicon carbide foamed ceramic to a muffle furnace, calcining the silicon carbide foamed ceramic for 6 hours at the temperature of 600 ℃, then placing the silicon carbide foamed ceramic in 1mol/L ammonium chloride solution at the temperature of 85 ℃ for 24 hours, and transferring the silicon carbide foamed ceramic to the muffle furnace, calcining the silicon carbide foamed ceramic for 4 hours at the temperature of 500 ℃ to obtain the high-dielectric composite microporous molecular sieve catalyst.
50g of high-dielectric composite microporous molecular sieve catalyst is filled in a quartz pipeline and placed in a microwave heating sleeve, and the microwave power is adjusted to control the catalytic temperature to be 450 ℃. Taking 100 g of Chinese tallow as a raw material, carrying out microwave pyrolysis on steam, passing through a quartz pipeline filled with a high-dielectric composite microporous molecular sieve catalyst, carrying out catalytic reforming and condensation to obtain 78.3 g of hydrocarbon-rich fuel oil, wherein the content of aromatic hydrocarbon and aromatic oxygen-containing compound is 80.9%.
Example 2.
The silicon carbide ceramic foam was calcined in a muffle furnace at 900 ℃ for 4 h. Then accurately weighing 25 g of 2 mol/L tetrapropyl ammonium hydroxide solution, 65 g of tetraethyl orthosilicate, 14 g of sodium chloride, 0.6 g of sodium aluminate and 1100 g of water, stirring strongly for 4h, and standing for 15 min to form gel; mixing the calcined silicon carbide foamed ceramic with gel according to the mass ratio of 1:2, putting the mixture into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into a microwave digestion instrument, controlling the microwave power to be 800W, controlling the temperature to be 160 ℃, and reacting for 3 hours; and washing the reacted silicon carbide foamed ceramic with distilled water for 5 times, transferring the silicon carbide foamed ceramic to a muffle furnace, calcining the silicon carbide foamed ceramic for 6 hours at the temperature of 600 ℃, then placing the silicon carbide foamed ceramic in 1mol/L ammonium chloride solution at the temperature of 85 ℃ for 24 hours, and transferring the silicon carbide foamed ceramic to the muffle furnace, calcining the silicon carbide foamed ceramic for 4 hours at the temperature of 500 ℃ to obtain the high-dielectric composite microporous molecular sieve catalyst.
50g of high-dielectric composite microporous molecular sieve catalyst is filled in a quartz pipeline and placed in a microwave heating sleeve, and the microwave power is adjusted to control the catalytic temperature to be 450 ℃. Taking 100 g of straws as a raw material, carrying out microwave pyrolysis on steam, passing through a quartz pipeline filled with a high-dielectric composite microporous molecular sieve catalyst, carrying out catalytic reforming and condensation to obtain 38.9 g of hydrocarbon-rich fuel oil, wherein the content of aromatic hydrocarbon and aromatic oxygen-containing compounds is 53%.
Example 3.
The silicon carbide foam ceramic is placed in a muffle furnace and calcined for 5 hours at 1000 ℃. Then accurately weighing 30 g of 2 mol/L tetrapropyl ammonium hydroxide solution, 70 g of tetraethyl orthosilicate, 12 g of sodium chloride, 0.5 g of sodium aluminate and 1000 g of water, stirring strongly for 4 hours, and standing for 15 min to form gel; mixing the calcined silicon carbide foamed ceramic with gel according to the mass ratio of 1:2, putting the mixture into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into a microwave digestion instrument, controlling the microwave power to be 800W, controlling the temperature to be 160 ℃, and reacting for 3 hours; and washing the reacted silicon carbide foamed ceramic with distilled water for 5 times, transferring the silicon carbide foamed ceramic to a muffle furnace, calcining the silicon carbide foamed ceramic for 6 hours at the temperature of 600 ℃, then placing the silicon carbide foamed ceramic in 1mol/L ammonium chloride solution at the temperature of 85 ℃ for 24 hours, and transferring the silicon carbide foamed ceramic to the muffle furnace, calcining the silicon carbide foamed ceramic for 4 hours at the temperature of 500 ℃ to obtain the high-dielectric composite microporous molecular sieve catalyst.
50g of high-dielectric composite microporous molecular sieve catalyst is filled in a quartz pipeline and placed in a microwave heating sleeve, and the microwave power is adjusted to control the catalytic temperature to be 450 ℃. Taking 100 g of soapstock as a raw material, carrying out microwave pyrolysis on steam, passing through a quartz pipeline filled with a high-dielectric composite microporous molecular sieve catalyst, carrying out catalytic reforming and condensation to obtain 67.6g of hydrocarbon-rich fuel oil, wherein the content of aromatic hydrocarbon and aromatic oxygen-containing compound is 90.8%.
Example 4.
The silicon carbide foam ceramic is placed in a muffle furnace and calcined for 5 hours at 1000 ℃. Then accurately weighing 30 g of 2 mol/L tetrapropyl ammonium hydroxide solution, 70 g of tetraethyl orthosilicate, 12 g of sodium chloride, 0.5 g of sodium aluminate and 1000 g of water, stirring strongly for 4 hours, and standing for 15 min to form gel; mixing the calcined silicon carbide foamed ceramic with gel according to the mass ratio of 1:2, putting the mixture into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into a microwave digestion instrument, controlling the microwave power to be 800W, controlling the temperature to be 160 ℃, and reacting for 3 hours; and washing the reacted silicon carbide foamed ceramic with distilled water for 5 times, transferring the silicon carbide foamed ceramic to a muffle furnace, calcining the silicon carbide foamed ceramic for 6 hours at the temperature of 600 ℃, then placing the silicon carbide foamed ceramic in 1mol/L ammonium chloride solution at the temperature of 85 ℃ for 24 hours, and transferring the silicon carbide foamed ceramic to the muffle furnace, calcining the silicon carbide foamed ceramic for 4 hours at the temperature of 500 ℃ to obtain the high-dielectric composite microporous molecular sieve catalyst.
50g of high-dielectric composite microporous molecular sieve catalyst is filled in a quartz pipeline and placed in a microwave heating sleeve, and the microwave power is adjusted to control the catalytic temperature to be 450 ℃. The method is characterized in that 100 g of dry sludge powder is used as a raw material, steam after microwave pyrolysis passes through a quartz pipeline filled with a high-dielectric composite microporous molecular sieve catalyst, 52.6g of hydrocarbon-rich fuel oil is obtained after catalytic reforming and condensation, and the content of aromatic hydrocarbon and aromatic oxygen-containing compounds is 60.7%.
Claims (1)
1. The application of the high-dielectric composite microporous molecular sieve catalyst is characterized in that: filling 50g of high-dielectric composite microporous molecular sieve catalyst into a quartz pipeline, placing the quartz pipeline into a microwave heating sleeve, and adjusting microwave power to control the catalytic temperature to be 450 ℃; taking 100 g of Chinese tallow as a raw material, carrying out microwave pyrolysis on steam, passing through a quartz pipeline filled with a high-dielectric composite microporous molecular sieve catalyst, carrying out catalytic reforming and condensation to obtain 78.3 g of hydrocarbon-rich fuel oil, wherein the content of aromatic hydrocarbon and aromatic oxygen-containing compound is 80.9%;
the preparation method of the high-dielectric composite microporous molecular sieve catalyst comprises the following steps: placing the silicon carbide foamed ceramic in a muffle furnace to be calcined for 4 hours at 900 ℃; then accurately weighing 25 g of 2 mol/L tetrapropyl ammonium hydroxide solution, 65 g of tetraethyl orthosilicate, 12 g of sodium chloride, 0.5 g of sodium aluminate and 1000 g of water, stirring strongly for 4 hours, and standing for 15 min to form gel; mixing the calcined silicon carbide foamed ceramic and gel according to the mass ratio of 1:2, putting the mixture into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into a microwave digestion instrument, controlling the microwave power to be 800W, controlling the temperature to be 160 ℃, and reacting for 3 hours; and washing the reacted silicon carbide foamed ceramic with distilled water for 5 times, transferring the silicon carbide foamed ceramic to a muffle furnace, calcining the silicon carbide foamed ceramic for 6 hours at the temperature of 600 ℃, then placing the silicon carbide foamed ceramic in 1mol/L ammonium chloride solution at the temperature of 85 ℃ for 24 hours, and transferring the silicon carbide foamed ceramic to the muffle furnace, calcining the silicon carbide foamed ceramic for 4 hours at the temperature of 500 ℃ to obtain the high-dielectric composite microporous molecular sieve catalyst.
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| CN201811145950.8A CN109261196B (en) | 2018-09-29 | 2018-09-29 | Preparation method of high-dielectric composite microporous molecular sieve catalyst |
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| CN102716762A (en) * | 2011-06-10 | 2012-10-10 | 中国科学院金属研究所 | Ultrafine molecular sieve structured catalytic material based on porous silicon carbide carrier and preparation thereof |
| CN103252253A (en) * | 2013-05-07 | 2013-08-21 | 中国科学院金属研究所 | Porous silicon-carbide carrier surface gradient pore molecular sieve coating and preparation method thereof |
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| CN101857462A (en) * | 2009-04-07 | 2010-10-13 | 中国科学院金属研究所 | Preparation method for molecular sieve coating material on porous silicon carbide ceramic surface |
| CN102716762A (en) * | 2011-06-10 | 2012-10-10 | 中国科学院金属研究所 | Ultrafine molecular sieve structured catalytic material based on porous silicon carbide carrier and preparation thereof |
| CN103252253A (en) * | 2013-05-07 | 2013-08-21 | 中国科学院金属研究所 | Porous silicon-carbide carrier surface gradient pore molecular sieve coating and preparation method thereof |
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| Silicon carbide foam supported ZSM-5 composite catalyst for microwave assisted pyrolysis of biomass;Zhou Nan et al;《BIORESOURCE TECHNOLOGY》;20180704;第267卷;第258页左栏第4段、第2.2节 * |
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