CN105498845B - A kind of supercritical CO2The CsPW/Zr-MCM-41 catalyst prepared in environment and its application - Google Patents
A kind of supercritical CO2The CsPW/Zr-MCM-41 catalyst prepared in environment and its application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 147
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 42
- 229910052792 caesium Inorganic materials 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 7
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000007598 dipping method Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 2
- 235000011187 glycerol Nutrition 0.000 description 48
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 15
- 239000012530 fluid Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- -1 alkali metal salt Chemical class 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019730 animal feed additive Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of supercritical COs241 catalyst of CsPW/Zr MCM prepared in environment, preparation method are with Zr MCM 41 for carrier, using supercritical CO2The acidic cs salts of heteropolyacid of dipping technique load 10~60%.Reach 65.2~100% using the catalyst glycerol conversion yield, acrolein selectivity reaches 56.8~85.4%.The invention also discloses application of aforementioned 41 catalyst of CsPW/Zr MCM in selective glycerol dehydration prepares methacrylaldehyde.Compared with prior art, the catalyst acidic cs salts of heteropolyacid that prepared by the method for the present invention dispersion degree on carrier is high, strong with carrier function power, and there is catalyst high hydrothermal stability, acidity to not easily run off.Meanwhile compared with existing product, the method for the present invention products obtained therefrom glycerol conversion yield and acrolein selectivity are high, long lifespan.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to supercritical CO2A CsPW/Zr-MCM-41 catalyst prepared in the environment and application thereof.
Background
With the increasing shortage of petroleum resources in the world, biodiesel which can be used as an alternative energy source is widely favored. The large amount of glycerol by-product, with its production increasing, leads to a market excess. Glycerol is an important biological renewable resource and has great application in the fields of medicines, foods, tobaccos, cosmetics and the like at present. Therefore, research into converting glycerol into high value-added products has been a hot spot.
Acrolein is an important organic synthesis intermediate and is mainly used in the fields of pharmaceutical synthesis, papermaking, coating, oil fields, organic synthesis industry and the like. The most important applications of acrolein at present are the synthesis of methionine as an animal feed additive and the preparation of 1, 3-propanediol; in addition, the method is also used for preparing essence, glutaraldehyde and the like. The current industrial production of acrolein is mainly the propylene oxidation process. However, the propylene oxidation method uses petroleum as an initial raw material, which not only does not meet the requirements of low-carbon economy, but also has the problem of competing for raw materials with other chemical products. The method for preparing the acrolein by the glycerol dehydration method takes renewable resources as raw materials, has simple process and strong competitive advantage and industrial application prospect. Therefore, it is receiving more and more extensive attention from academia and industry.
Watanabe M et al examined glycerol concentration, reaction pressure, temperature and H under hot water pressure2SO4The effect of concentration on the performance of the glycerol dehydration reaction, the results show that high concentrations of glycerol and H2SO4And higher pressure and temperature, both favor acrolein formation, at optimum conditions: under the conditions of 400 ℃ and 34.5MPa, the conversion rate reaches 90 percent, and the selectivity reaches 80 percent, which shows that the acid condition promotes the reaction for preparing the acrolein by glycerol dehydration. However, the liquid acid catalytic reaction has the disadvantages of harsh reaction conditions, corrosion on equipment, easy degradation of products, incapability of separating liquid acid from a reaction system and the like.
Patent US2558520 discloses H loaded with diatomaceous earth3PO4The patent of catalytic gas phase or liquid phase dehydration of glycerol shows acrolein selectivity of 72%. But the catalyst deactivated rapidly.
Patents US5426249 and US1034803C report the dehydration of glycerol over a phosphoric acid catalyst supported on alumina, HZSM-5, HY, etc., with a glycerol conversion of only 19% when the acrolein selectivity was about 71%. It is likely that at high temperatures, glycerol polymerizes on the catalyst surface covering the active sites of the catalyst, resulting in very low glycerol conversion.
Chinese patent document CN201019026084.5 proposes a method for preparing acrolein in a fixed bed micro reaction device by using heteropolyacid-supported alumina, diatomaceous earth, activated carbon, rutile type titanium dioxide and kaolin, wherein the conversion rate of glycerol is 13.5-80.6%, and the selectivity of acrolein is 49.0-90.5%. However, the catalyst is easy to deactivate, and the carbon deposition in a short reaction time seriously leads to short service life of the catalyst.
Patent document CN201210128727.9 reports that when acrolein is produced by catalytic liquid phase dehydration of glycerin using a catalyst of alkali metal salt of heteropoly-acid (potassium salt, rubidium salt, cesium salt) by reactive rectification technique, the conversion rate of glycerin reaches up to 100%, the yield of acrolein is 58.9 to 78.2%, and the yields of hydroxyacetone and acetic acid as by-products are both less than 10%. Although the catalyst can obtain higher glycerol conversion rate and acrolein yield in the initial reaction stage, the catalyst is easy to generate carbon deposition and deactivate, and has poor stability and short service life.
In the above-mentioned patent documents, although the green and environment-friendly solid acid catalysts are adopted, the corrosion to the equipment is reduced to a certain extent, and higher glycerol conversion rate and acrolein yield can be obtained in a short time, the catalyst surface is prone to serious carbon deposition, and the catalyst deactivation rate is high. How to more effectively inhibit carbon deposition, prolong the service life of the catalyst and simultaneously ensure higher glycerol conversion rate and acrolein selectivity is the basis for realizing industrial production.
The supercritical fluid technology is rapidly developed in recent years, the supercritical fluid refers to a special fluid above the critical temperature and the critical pressure, the property of the supercritical fluid is between that of gas and liquid, and the supercritical fluid has the viscosity and the diffusion coefficient similar to those of the gas, so that the supercritical fluid has good performances of flowing, mass transfer, heat transfer and the like; the supercritical fluid has the dissolving capacity and heat transfer coefficient similar to those of liquid, and the dissolving capacity of the supercritical fluid to solid is 10-100 times higher than that of gas; the supercritical fluid has good miscibility with gas; the supercritical fluid has very low surface tension, so that the supercritical fluid has excellent surface wetting property and penetrating capability. Because the supercritical fluid has the characteristics of high diffusivity, strong solubility, excellent surface wettability, continuously adjustable physicochemical properties and the like, the supercritical fluid becomes a potential good medium in the fields of extraction separation, various chemical reactions, material preparation and the like, and shows wide application prospects. Using supercritical fluids, especially supercritical CO2The technical preparation of supported catalytic materials has become a hotspot for researching and preparing novel materials at home and abroad.
The patent uses glycerin as raw material to generate the thirdIn the olefine aldehyde process, Zr-MCM-41 is used as a carrier, and supercritical CO is adopted2The supported heteropolyacid cesium salt catalyst is synthesized by an impregnation technology, and the heteropolyacid cesium salt has high dispersion degree on the surface of a carrier, strong action with the carrier and good hydrothermal stability. The glycerin water solution is pumped into the fixed bed reactor through a micro pump, and certain airspeed is controlled. The conversion rate of the glycerol and the selectivity of the acrolein are effectively improved, the generation of carbon deposition is inhibited, and the service life of the catalyst is long.
Disclosure of Invention
The technical problem to be solved by the invention is to provide supercritical CO2The CsPW/Zr-MCM-41 catalyst prepared in the environment solves the problems of low glycerol conversion rate and acrolein selectivity and short service life of the catalyst in the prior art.
The technical problem to be solved by the invention is to provide a preparation method of the catalyst.
The technical problem to be solved finally by the invention is to provide the application of the catalyst in the reaction for preparing the acrolein by selectively dehydrating the glycerol.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
supercritical CO2A method for preparing a CsPW/Zr-MCM-41 catalyst in the environment comprises the following steps:
(1) dissolving a cesium source and heteropoly acid in deionized water, and uniformly mixing to obtain a heteropoly acid cesium salt aqueous solution; soaking the Zr-MCM-41 carrier in aqueous solution of cesium heteropoly acid salt, and stirring to obtain uniform slurry;
(2) heating the uniform slurry obtained in the step (2) in a closed reaction container to a supercritical temperature, and pumping CO into the reaction container by using a high-pressure injection pump2The gas makes the container reach a certain pressure to perform supercritical treatment; after the supercritical treatment is finished, cooling, decompressing and collecting a product;
(3) and (4) centrifugally separating the product obtained in the step (3), drying the solid part of the lower layer, and roasting to obtain the cesium heteropoly acid salt/Zr-MCM-41 catalyst.
In the step (1), the cesium source is cesium carbonate or cesium nitrate, preferably cesium carbonate; the heteropoly acid is phosphotungstic acid, silicotungstic acid, phosphomolybdic acid or silicomolybdic acid.
In the step (1), the mol ratio of cesium to heteropoly acid in the cesium source is 0.5-3: 1, preferably 2.5: 1.
in the step (1), the amount of the water is based on the amount capable of completely dissolving the cesium source, the heteropoly acid and the Zr-MCM-41 carrier.
In the step (1), the Zr-MCM-41 carrier can be obtained by the market, and can also be prepared by the following method:
mixing a zirconium source and a silicon source to obtain a mixed system I for later use, dissolving a template agent in water, and uniformly mixing the template agent with an ammonia water solution to obtain a mixed system II for later use; and dropwise adding the mixed system I into the mixed system II under continuous stirring, stirring at room temperature for 2-5 h, crystallizing at 80-100 ℃ for 40-50 h, cooling, filtering, washing the solid part, drying, and roasting to obtain the Zr-MCM-41 carrier.
Wherein,
the zirconium source is preferably zirconium n-propoxide;
the silicon source is preferably tetraethoxysilane;
the template agent is cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride or cetyl triethyl ammonium bromide, and the ammonia water solution is 28 wt% ammonia water solution;
the molar ratio of zirconium in the zirconium source to silicon in the silicon source to the template to ammonia in the ammonia water solution is 0.05-0.2: 1: 0.3-0.4: 8;
the mol ratio of the template agent to the water used for dissolving the template agent is 1: 150 to 200 parts;
the aqueous ammonia solution is preferably a 28 wt% aqueous ammonia solution.
In the preparation method of the Zr-MCM-41 carrier, the washing method comprises the steps of washing the solid part for 3-5 times by using deionized water; the drying method is drying for 8-12 h at 80-110 ℃, preferably for 12 h; the roasting method is roasting for 3-6 h, preferably 6h at 400-600 ℃.
In the step (2), the supercritical treatment method is carried out at 30-150 ℃ and under 7-16 Mpa for 1-6 h.
In the step (3), the centrifugal separation condition is 3000-8000 rpm for 5-20 min.
In the step (3), the drying method is drying for 3-6 h, preferably 3h at 80-120 ℃; the roasting method is roasting for 2-5 h, preferably 3h at 300-500 ℃.
In the step (3), in the obtained cesium heteropolyacid salt/Zr-MCM-41 catalyst, the loading amount of the cesium heteropolyacid salt is 10-60 wt% (the loading amount refers to the weight ratio of the cesium heteropolyacid salt to the cesium heteropolyacid salt/Zr-MCM-41 catalyst).
The CsPW/Zr-MCM-41 catalyst prepared by any one of the preparation methods is also within the protection scope of the invention.
The application of the CsPW/Zr-MCM-41 catalyst in the preparation of acrolein by selective dehydration of glycerol is also within the protection scope of the invention.
Has the advantages that:
compared with the prior art, the invention has the following advantages:
in the aspect of selecting raw material glycerin, not only industrial pure glycerin can be selected, but also crude glycerin prepared by biodiesel can be selected, and the raw material sources are wide; the catalyst cesium heteropoly acid salt prepared by the supercritical dipping method has high dispersity, strong acting force with a Zr-MCM-41 carrier, high hydrothermal stability and difficult loss of acidity; high conversion rate of glycerin and selectivity of acrolein, and long service life.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1
Synthesis of Zr — MCM-41(Si/Zr ═ 5) support: mixing and stirring 9.1ml of zirconium n-propoxide and 22.8ml of ethyl orthosilicate to obtain a mixed system I for later use; dissolving 12.2g of hexadecyl trimethyl ammonium chloride in 100ml of deionized water, and uniformly mixing with 110ml of 28 wt% ammonia water solution to obtain a mixed system II for later use; dropwise adding the mixed system I into the mixed system II under continuous stirring, stirring at room temperature for 2h at 500r/min until gel is formed, transferring the mixed system into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, placing the kettle in an oven at 80 ℃ for heating for 40h, and cooling to room temperature; filtering the mixed solution in the reaction kettle, taking the solid part, washing the solid part for 3 times by using deionized water, and then placing the solid in a drying box at 80 ℃ for drying for 10 hours; and roasting the dried solid in a muffle furnace at 450 ℃ for 3h to obtain the Zr-MCM-41 (Si/Zr-5) carrier.
Synthesis of 20 wt% cesium phosphotungstate/Zr-MCM-41 (Si/Zr ═ 5): 0.043gCs is added into a reaction kettle2CO3And 0.302g of phosphotungstic acid in 20ml of deionized water, then 1.5g of Zr-MCM-41 (Si/Zr-5) carrier is soaked in the solution, the mixture is stirred evenly to obtain uniform slurry, the temperature of the reaction kettle is raised to 80 ℃ by adopting the programmed temperature rise, and then a high-pressure injection pump is used for pumping CO into the reaction kettle2Filling gas to make the pressure in the kettle reach 8MPa, and maintaining the supercritical condition for 2 h; after the supercritical treatment is finished, cooling, relieving pressure, unloading the kettle, collecting a sample, centrifugally separating for 5min at 3000r/min, taking a lower-layer solid part, drying for 3h in an oven at 80 ℃, and roasting for 3h in a muffle furnace at 300 ℃ to obtain 20 wt% cesium phosphotungstate/Zr-MCM-41 (Si/Zr ═ 5) catalytic reaction productAnd (3) preparing.
The performance evaluation of the catalyst adopts a fixed bed reactor, 10 wt% of glycerol aqueous solution is taken as a raw material, the dosage of 20 wt% of cesium phosphotungstate/Zr-MCM-41 catalyst is 0.5g, the reaction temperature is 280 ℃, and the mass space velocity is 0.5h-1Then, after reacting for 2h, the conversion rate of the glycerol is 87.2 percent, and the selectivity of the acrolein is 70.5 percent; after 10h of reaction, the glycerol conversion was 84.0% and the acrolein selectivity was 68.4%.
Example 2
Synthesis of Zr — MCM-41(Si/Zr ═ 7) support: mixing and stirring 6.5ml of zirconium n-propoxide and 22.8ml of ethyl orthosilicate to obtain a mixed system I for later use; dissolving 12.2g of hexadecyl triethyl ammonium bromide in 110ml of deionized water, and uniformly mixing with 110ml of 28 wt% ammonia water solution to obtain a mixed system II for later use; dropwise adding the mixed system I into the mixed system II under continuous stirring, stirring at room temperature for 3h at 500r/min until gel is formed, transferring the mixed system into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, placing the kettle in a drying oven at 100 ℃ for heating for 45h, and cooling to room temperature; filtering the mixed solution in the reaction kettle, taking the solid part, washing the solid part with deionized water for 4 times, and then placing the solid in a drying oven at 100 ℃ for drying for 12 hours; the dried solid was calcined in a muffle furnace at 500 ℃ for 4 hours to obtain a Zr-MCM-41(Si/Zr ═ 7) support.
Synthesis of 30 wt% cesium silicotungstate/Zr-MCM-41 (Si/Zr ═ 7): dissolving 0.049g of cesium nitrate and 0.347g of silicotungstic acid in 30ml of deionized water in a reaction kettle, then soaking 1g of Zr-MCM-41(Si/Zr ═ 7) carrier in the solution, stirring uniformly to obtain uniform slurry, raising the temperature of the reaction kettle to 100 ℃ by adopting programmed heating, and then using a high-pressure injection pump to inject CO into the reaction kettle2Filling gas to make the pressure in the kettle reach 8MPa, and maintaining the supercritical condition for 4 h; and after the supercritical treatment is finished, cooling, relieving pressure, unloading the kettle, collecting a sample, centrifugally separating for 10min at 5000r/min, taking a lower-layer solid part, drying for 4h in an oven at 100 ℃, and roasting for 4h in a muffle furnace at 350 ℃ to obtain the 30 wt% cesium silicotungstate/Zr-MCM-41 (Si/Zr ═ 7) catalyst.
The performance evaluation of the catalyst adopts a fixed bed reactor, 20 wt% of glycerol aqueous solution is taken as a raw material, the dosage of 30 wt% of cesium silicotungstate/Zr-MCM-41 catalyst is 0.5g, the reaction temperature is 300 ℃, and the mass space velocity is 1.0h-1Then, after reacting for 2 hours, the conversion rate of the glycerol is 85.2 percent, and the selectivity of the acrolein is 63.5 percent; after 10h of reaction, the conversion of glycerol was 82.8% and the selectivity to acrolein was 61.6%.
Example 3
Synthesis of Zr — MCM-41(Si/Zr ═ 10) support: mixing and stirring 4.5ml of zirconium n-propoxide and 22.8ml of ethyl orthosilicate to obtain a mixed system I for later use; dissolving 12.2g of hexadecyl trimethyl ammonium bromide in 100ml of deionized water, and uniformly mixing with 110ml of 28 wt% ammonia water solution to obtain a mixed system II for later use; dropwise adding the mixed system I into the mixed system II under continuous stirring, stirring at room temperature for 4h at 500r/min until gel is formed, transferring the mixed system into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, placing the kettle in an oven at 80 ℃ for heating for 50h, and cooling to room temperature; filtering the mixed solution in the reaction kettle, taking the solid part, washing the solid part with deionized water for 5 times, and then placing the solid in a drying oven at 100 ℃ for drying for 10 hours; the dried solid was calcined in a muffle furnace at 550 ℃ for 5 hours to obtain a Zr-MCM-41(Si/Zr ═ 10) support.
Synthesis of 30 wt% cesium phosphomolybdate/Zr-MCM-41 (Si/Zr ═ 10): 0.081gCs is added into a reaction kettle2CO3And 0.364g of phosphomolybdic acid in 40ml of deionized water, then 1g of Zr-MCM-41(Si/Zr ═ 10) carrier is immersed in the solution, the solution is stirred evenly to obtain uniform slurry, the temperature of the reaction kettle is raised to 100 ℃ by adopting programmed temperature rise, and then CO is injected into the reaction kettle by using a high-pressure injection pump2Filling gas to make the pressure in the kettle reach 12MPa, and maintaining the supercritical condition for 4 h; after the supercritical processing is finished, cooling, decompressing, discharging the kettle, collecting a sample, centrifugally separating for 15min at 8000r/min, taking a lower-layer solid part, drying for 5h at 120 ℃ in an oven, roasting for 5h at 400 ℃ in a muffle furnace to obtain 30 wt% cesium phosphomolybdate/Zr-MCM-41(Si/Zr ═ 10) catalyst.
The performance evaluation of the catalyst adopts a fixed bed reactor, 10 wt% of glycerol aqueous solution is taken as a raw material, the dosage of 30 wt% of cesium phosphomolybdate/Zr-MCM-41 catalyst is 0.5g, the reaction temperature is 340 ℃, and the mass space velocity is 0.6h-1Then, after reacting for 2 hours, the conversion rate of the glycerol is 65.2 percent, and the selectivity of the acrolein is 58.5 percent; after 10h of reaction, the conversion of glycerol was 60.8% and the selectivity to acrolein was 56.8%.
Example 4
Synthesis of Zr — MCM-41(Si/Zr ═ 15) support: mixing and stirring 3.0ml of zirconium n-propoxide and 22.8ml of ethyl orthosilicate to obtain a mixed system I for later use; dissolving 12.2g of hexadecyl trimethyl ammonium bromide in 110ml of deionized water, and uniformly mixing with 110ml of 28 wt% ammonia water solution to obtain a mixed system II for later use; dropwise adding the mixed system I into the mixed system II under continuous stirring, stirring at room temperature for 2h at 500r/min until gel is formed, transferring the mixed system into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, placing the kettle in a drying oven at 100 ℃, heating for 50h, and cooling to room temperature; filtering the mixed solution in the reaction kettle, taking the solid part, washing the solid part with deionized water for 4 times, and then placing the solid in a drying oven at 80 ℃ for drying for 12 hours; the dried solid was calcined in a muffle furnace at 600 ℃ for 6 hours to obtain a Zr-MCM-41(Si/Zr ═ 15) support.
Synthesis of 50 wt% Cesium phosphotungstate/Zr-MCM-41 (Si/Zr ═ 15): 0.114gCs in the reaction kettle2CO30.806g of phosphotungstic acid is dissolved in 40ml of deionized water, 1g of Zr-MCM-41(Si/Zr ═ 15) carrier is soaked in the solution and is evenly stirred to obtain even slurry, the temperature of the reaction kettle is raised to 80 ℃ by adopting programmed temperature, and then CO is injected into the reaction kettle by a high-pressure injection pump2Filling gas to make the pressure in the kettle reach 10MPa, and maintaining the supercritical condition for 4 h; after the supercritical treatment is finished, cooling, decompressing, unloading the kettle to collect a sample, centrifugally separating for 10min at 8000r/min, taking the lower solid part, drying for 3h at 110 ℃ in an oven, roasting for 3h at 300 ℃ in a muffle furnace to obtain 50 wt% of phosphorusCesium tungstate/Zr-MCM-41 (Si/Zr ═ 15) catalyst.
The performance evaluation of the catalyst adopts a fixed bed reactor, 20 wt% of glycerol aqueous solution is taken as a raw material, the dosage of 50 wt% of cesium phosphotungstate/Zr-MCM-41 catalyst is 0.5g, the reaction temperature is 320 ℃, and the mass space velocity is 0.4h-1Then, after reacting for 2 hours, the conversion rate of the glycerol is 100 percent, and the selectivity of the acrolein is 85.4 percent; after 10h of reaction, the conversion rate of glycerol was 96.8% and the selectivity of acrolein was 80.0%.
According to the catalyst preparation method reported in patent CN 201210480141.9: vacuum impregnation method. We used this method to prepare the catalyst and compare the methods referred to in this patent. 0.114gCs2CO3Dissolving in 40ml deionized water, adding 1g Zr-MCM-41(Si/Zr ═ 15) carrier synthesized by us into the aqueous solution, stirring, treating at room temperature for 1h by vacuum impregnation method, and adding Cs2CO3Soaking the solution at normal pressure for 24h, and drying at 110 deg.C for 10 h; and then 0.806g of phosphotungstic acid is dissolved in 30ml of deionized water, the mixture is stirred and then treated for 1h at room temperature by adopting a vacuum impregnation method, the obtained supported catalyst carrier is then added with a phosphotungstic acid solution and is immersed for 24h at normal pressure, the solution is filtered and washed, and is dried for 10h at 110 ℃, and is roasted for 3h at 300 ℃ to obtain the cesium phosphotungstate supported catalyst. The activity of the reaction mixture in the reaction for producing acrolein by dehydration of glycerin was evaluated under the same reaction conditions as in example 4. After reacting for 2h, the conversion rate of glycerol is 96.4%, the selectivity of acrolein is 80.2%, after reacting for 10h, the conversion rate of glycerol is 70.1%, and the selectivity of acrolein is 72.8%.
The activity of the catalyst prepared in the patent is higher than that of the catalyst prepared according to the CN201210480141.9 patent, and the stability is high. Through the comparative analysis of characterization results, the cesium heteropolyacid salt on the catalyst prepared by the method has high dispersity on the Zr-MCM-41 carrier, strong acting force with the carrier and high hydrothermal stability.
Example 5
Synthesis of Zr — MCM-41(Si/Zr ═ 20) support: mixing and stirring 2.3ml of zirconium n-propoxide and 22.8ml of ethyl orthosilicate to obtain a mixed system I for later use; uniformly mixing 12.2g of hexadecyl triethyl ammonium bromide and 100ml of deionized water with 110ml of 28 wt% ammonia water solution to obtain a mixed system II for later use; dropwise adding the mixed system I into the mixed system II under continuous stirring, stirring at room temperature for 5h at 500r/min until gel is formed, transferring the mixed system into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, placing the kettle in an oven at 80 ℃ for heating for 50h, and cooling to room temperature; filtering the mixed solution in the reaction kettle, taking the solid part, washing the solid part for 3 times by using deionized water, and then placing the solid in a drying oven at 110 ℃ for drying for 12 hours; the dried solid was calcined in a muffle furnace at 500 ℃ for 6 hours to obtain a Zr-MCM-41(Si/Zr ═ 20) support.
Synthesis of 40 wt% cesium phosphotungstate/Zr-MCM-41 (Si/Zr ═ 20): 0.076gCs is added into a reaction kettle2CO3And 0.537g of phosphotungstic acid are dissolved in 30ml of deionized water, 1g of Zr-MCM-41(Si/Zr ═ 20) carrier is soaked in the solution, the mixture is stirred evenly to obtain uniform slurry, the temperature of the reaction kettle is raised to 120 ℃ by adopting programmed temperature rise, and then CO is injected into the reaction kettle by a high-pressure injection pump2Filling gas to make the pressure in the kettle reach 14MPa, and maintaining the supercritical condition for 6 h; and after the supercritical treatment is finished, cooling, relieving pressure, unloading the kettle, collecting a sample, centrifugally separating for 15min at 5000r/min, taking a lower-layer solid part, drying for 3h in an oven at 100 ℃, and roasting for 3h in a muffle furnace at 450 ℃ to obtain the 40 wt% cesium phosphotungstate/Zr-MCM-41 (Si/Zr ═ 20) catalyst.
The performance evaluation of the catalyst adopts a fixed bed reactor, the 20 wt% glycerol aqueous solution is used as the raw material, the dosage of the catalyst is 0.5g, the reaction temperature is 340 ℃, and the mass space velocity is 1.5h-1Then, the performance evaluation of the catalyst adopts a fixed bed reactor, 10 wt% of glycerol aqueous solution is taken as a raw material, the dosage of 40 wt% of cesium phosphotungstate/Zr-MCM-41 catalyst is 0.5g, the reaction temperature is 320 ℃, and the mass space velocity is 0.8h-1After 2h of reaction, the conversion rate of glycerol is 98.4%, and the selectivity of acrolein is82.6 percent; after 10h of reaction, the conversion of glycerol was 93.8% and the selectivity to acrolein was 77.2%.
Claims (8)
1. Supercritical CO2A method for preparing a cesium heteropolyacid salt/Zr-MCM-41 catalyst in an environment, comprising the steps of:
(1) dissolving a cesium source and heteropoly acid in water, and uniformly mixing to obtain a heteropoly acid cesium salt water solution; soaking the Zr-MCM-41 carrier in aqueous solution of cesium heteropoly acid salt, and stirring to obtain uniform slurry;
(2) heating the uniform slurry obtained in the step (1) in a closed reaction container and pumping CO into the reaction container2Gas to perform supercritical processing(ii) a After the supercritical treatment is finished, cooling, decompressing and collecting a product;
(3) centrifugally separating the product obtained in the step (2), taking a lower-layer solid part, drying and roasting to obtain the cesium heteropoly acid salt/Zr-MCM-41 catalyst;
in the step (1), the Zr-MCM-41 carrier is prepared by the following method:
mixing a zirconium source and a silicon source to obtain a mixed system I for later use, dissolving a template agent in water, and uniformly mixing the template agent with an ammonia water solution to obtain a mixed system II for later use; dropwise adding the mixed system I into the mixed system II under continuous stirring, stirring at room temperature for 2-5 h, crystallizing at 80-100 ℃ for 40-50 h, cooling, filtering, washing the solid part, drying, and roasting to obtain a Zr-MCM-41 carrier;
in the step (2), the supercritical treatment method is carried out at 30-150 ℃ and under 7-16 Mpa for 1-6 h.
2. The method according to claim 1, wherein in step (1), the cesium source is cesium carbonate or cesium nitrate, and the heteropolyacid is phosphotungstic acid, silicotungstic acid, phosphomolybdic acid or silicomolybdic acid.
3. The preparation method according to claim 1, wherein in the step (1), the molar ratio of cesium to heteropoly acid in the cesium source is 0.5 to 3: 1.
4. the method according to claim 1, wherein the centrifugation in the step (3) is carried out under a condition of 3000 to 8000 rpm for 5 to 20 minutes.
5. The preparation method according to claim 1, wherein in the step (3), the drying method is drying at 80-120 ℃ for 3-6 h; the roasting method is roasting for 2-5 hours at 300-500 ℃.
6. The preparation method according to claim 1, wherein in the step (3), the cesium heteropolyacid salt/Zr-MCM-41 catalyst is loaded in an amount of 10-60 wt%.
7. The cesium heteropolyacid salt/Zr-MCM-41 catalyst prepared by the method of any one of claims 1-6.
8. Use of the cesium heteropolyacid salt/Zr-MCM-41 catalyst of claim 7 in the selective dehydration of glycerol to acrolein.
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