CN114471644B - Porous heteropolyacid catalyst and preparation method and application thereof - Google Patents
Porous heteropolyacid catalyst and preparation method and application thereof Download PDFInfo
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- CN114471644B CN114471644B CN202011163252.8A CN202011163252A CN114471644B CN 114471644 B CN114471644 B CN 114471644B CN 202011163252 A CN202011163252 A CN 202011163252A CN 114471644 B CN114471644 B CN 114471644B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 27
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910001868 water Inorganic materials 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 5
- -1 alkyl chain quaternary ammonium salt Chemical class 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- NRKQBMOGOKEWPX-UHFFFAOYSA-N vanadyl nitrate Chemical compound [O-][N+](=O)O[V](=O)(O[N+]([O-])=O)O[N+]([O-])=O NRKQBMOGOKEWPX-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000007789 gas Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910017299 Mo—O Inorganic materials 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 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
- 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
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a porous heteropolyacid catalyst and a preparation method thereof, wherein the porous heteropolyacid catalyst comprises heteropolyacid and a carrier, and is obtained by assembling an organic template agent and the carrier under an alkaline condition, further mixing and drying the organic template agent and the heteropolyacid, and then roasting the organic template agent and the carrier in an inert gas atmosphere and then roasting the organic template agent and the carrier in an oxygen-containing atmosphere. The porous heteropoly acid catalyst can be used for preparing methacrylic acid by selectively oxidizing methacrolein, so that the methacrolein is subjected to oxidation reaction in the presence of mixed gas of oxygen and nitrogen and water to generate the methacrylic acid. The catalyst of the invention maintains higher single pass yield of methacrylic acid for a long time under higher load, the conversion rate of the methacrylic aldehyde can reach more than 70%, and the selectivity of the methacrylic acid can reach more than 84%.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a porous heteropolyacid catalyst for methacrylic acid synthesis and a preparation method thereof.
Background
The heteropoly compound has good acid site and oxidation-reduction performance, is a widely used catalyst, and has been industrially applied in the fields of olefin hydration, bisphenol A synthesis, methacrylic acid preparation by methacrolein oxidation and the like. Most of heteropoly compounds synthesized by the traditional hydrothermal method have no uniform mesoscopic pore structure, and the specific surface area is very low, so that the contact between the active site of the heteropoly compound and a substrate is insufficient, and the activity of the catalyst is reduced. The specific surface area of the porous heteropoly compound prepared by the template agent can be improved, but the removal of the template agent is a relatively troublesome problem. The conventional method for removing the template agent comprises a solvent extraction method and a roasting method, wherein the organic template agent is dissolved and removed by heating and refluxing in an organic solvent, the method is carried out at a lower temperature, so that the stability of a heteropolyacid structure can be ensured, but a large amount of organic solvent is required, the production process cost is increased, and meanwhile, the heteropolyacid catalyst maintains the stability of the structure in the preparation process, but the structure is easy to collapse when the heteropolyacid catalyst is used in catalytic reactions with higher temperatures; the latter is to remove the template agent by high-temperature roasting in an oxygen-containing atmosphere, and because the Keggin structure heteropolyanion of the heteropolyacid has poor thermal stability at a higher temperature, the method can directly lead to collapse of the heteropolyanion structure to form a compact oxide, and the compact oxide does not have a porous structure any more.
Therefore, how to ensure the high specific surface area and the porous structure of the heteropoly compound catalyst and the thermal stability of the catalyst is an important research direction in the field. US4621155A proposes adding an organic base during precipitation to increase the specific surface area of the catalyst and to regulate the pore size distribution, and the catalyst prepared by this method can improve the yield of methacrylic acid to some extent during the preparation of methacrylic acid, but has limited effect. The heteropoly acid compound is loaded on the porous carrier, so that the specific surface area of the catalyst can be increased, and the utilization rate of the active components can be improved. US3939096a reports a catalyst using porous silica as a carrier, which has good catalytic performance for the reaction of preparing acrylic acid by oxidizing acrolein, but has poor catalytic effect for the oxidation reaction of methacrolein. The anion unit size of the heteropoly acid compound is larger, the microporous material is used as the carrier, the loading is difficult to carry out by using the surface of the inner hole, and particularly, the blocking of the carrier pore canal can be serious under high loading. CN110694687A proposes a supported nano heteropoly acid catalyst with large pore size silica of 50-500 nm as carrier, and the supported active component heteropoly acid has particle size of 4-10 nm and high selectivity and stability to catalyze the oxidation reaction of methacrolein. However, the large-aperture silica carrier in the method is prepared by a polymer gel crystal template method, has very complicated steps, and is not suitable for large-scale industrial production.
Disclosure of Invention
The invention provides a porous heteropolyacid catalyst with higher specific surface area and thermal stability, a preparation method and application thereof, and aims to solve the problems of low specific surface area, poor thermal stability and the like of the heteropolyacid catalyst. Namely, a first object of the present invention is to provide a porous heteropolyacid catalyst comprising a heteropolyacid and a support, wherein the active elements of the heteropolyacid comprise one or more of Mo, V and P, and the support comprises a silicon-based porous support;
The porous heteropolyacid catalyst is obtained by assembling an organic template agent and a carrier under alkaline conditions, mixing the organic template agent with the heteropolyacid, drying, and roasting twice in an inert gas atmosphere and an oxygen-containing atmosphere.
According to some embodiments of the invention, the precursor of elemental Mo comprises H 3PMo12O40 or H 4PMo11VO40.
According to some embodiments of the invention, the precursor of element V comprises one or more of vanadyl sulfate, vanadyl oxalate, vanadyl acetylacetonate, V 2O5, or vanadyl nitrate.
According to some embodiments of the invention, the support comprises silica; preferably, the precursor of the silicon dioxide comprises one or more of silicate, silicate ester and organosilane. According to some embodiments of the invention, the precursor of silica comprises ethyl orthosilicate, methyl orthosilicate.
According to some embodiments of the invention, the organic templating agent comprises amphiphilic alkyl chain quaternary ammonium salts or polyether amphiphilic block copolymers. According to some embodiments of the invention, the organic template comprises one or more of cetyltrimethylammonium bromide, P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), F127 (polyoxyethylene-polyoxypropylene ether block copolymer).
According to some embodiments of the invention, the organic templating agent comprises cetyltrimethylammonium bromide.
According to some embodiments of the invention, the mass of the organic template and the carrier is 0.005-0.05, and according to some embodiments of the invention, the mass of the organic template and the carrier is 0.01-0.03.
According to some embodiments of the invention, the mass ratio of the heteropoly acid to the carrier is 0.1-1.0. According to some embodiments of the invention, the mass ratio of the heteropoly acid to the carrier is 0.5-1.0.
According to some embodiments of the invention, the porous heteropolyacid catalyst has a specific surface area of 80 to 120m 2/g and an average pore diameter of 3 to 8nm.
A second object of the present invention is to provide a method for producing the above porous heteropolyacid catalyst, comprising mixing and drying a heteropolyacid and a support in the presence of an organic template agent, followed by performing a first calcination in an inert gas atmosphere and a second calcination in an oxygen-containing atmosphere.
According to some embodiments of the invention, the method of mixing and drying the heteropolyacid with the support in the presence of the organic template further comprises the steps of:
(1) Heating and dissolving the heteropoly acid precursor;
(2) Dissolving an organic template agent, slowly adding a silicon dioxide precursor and an alkali solution at one time under the condition of low-speed stirring, and adjusting the pH to be slightly alkaline;
(3) Raising the stirring speed, adding the heteropoly acid precursor solution obtained in the step (1) into the mixed solution obtained in the step (2), and continuously heating, refluxing and stirring;
(4) Evaporating the slurry obtained in the step (3) by a rotary evaporation method to obtain powder; and roasting the powder twice to obtain the catalyst.
According to some embodiments of the invention, the stirring speed of the low-speed stirring in the step (2) is 60-220 rpm; according to some embodiments of the invention, the low speed stirring is at a stirring speed of 120 to 180rpm.
According to some embodiments of the invention, the rate of addition of the silica precursor in step (2) is 0.5-10 mL/min; according to some embodiments of the invention, the rate of addition of the silica precursor is 2 to 4mL/min.
According to some embodiments of the invention, the alkaline solution of step (2) is selected from the group consisting of ammonia, sodium hydroxide solution, potassium hydroxide solution; according to some embodiments of the invention, the alkaline solution of step (2) is preferably aqueous ammonia.
According to some embodiments of the invention, the stirring speed of step (3) is increased to 220-800 rpm.
According to some embodiments of the invention, the heating reflux temperature in step (3) is 60-120 ℃ and the heating time is 0.5-2 h.
According to some embodiments of the invention, the rotary evaporation heating temperature in the step (4) is 80-150 ℃, the heating time is 0.5-10 h, and the stirring speed is 220-800 rpm.
According to some embodiments of the invention, the inert gas used for the first calcination comprises nitrogen, argon or helium.
According to some embodiments of the invention, the inert gas used in the first calcination comprises nitrogen, argon or helium having a purity of 99.99% or more.
According to some embodiments of the invention, the first firing is at a temperature of 250-450 ℃, at a rate of 5 ℃/min, and for a firing time of 1-5 hours.
According to some embodiments of the invention, the second calcination is performed rapidly under an oxygen-containing atmosphere, the calcination temperature is 180-600 ℃, the heating rate is 10 ℃/min, and the calcination time is 20-60 min.
The invention also aims to provide the application of the porous heteropoly acid catalyst in the preparation of methacrylic acid by the selective oxidation of methacrolein.
According to some embodiments of the invention, the use comprises oxidizing methacrolein in the presence of a mixed gas of oxygen and nitrogen and water to produce methacrylic acid using the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention is based on the following findings, and the inventor provides a method for performing heat treatment by two-step roasting to solve the problems that the heteropolyanion structure of a porous heteropolyacid catalyst and the pore channel structure of the catalyst are damaged in the heat treatment process. After the dry powder is obtained through rotary evaporation, the first step is roasting in an inert gas atmosphere, and the purpose of the first step is to carbonize the template agent, so that the obtained carbon and the silica carrier together play a good role in stabilizing and protecting the structure and the porous framework of the heteropoly acid, and the direct structural collapse of the heteropoly acid is avoided to form metal oxides. The second step is quick roasting in an oxygen-containing atmosphere, the purpose of which is to remove the carbon obtained in the last step and avoid the reduction of the catalyst activity caused by covering the surface of the active component, in the step, the residual carbon in the last step is favorable for maintaining the stable structure of heteropolyacid, meanwhile, the quick heating and short-time roasting can avoid or reduce the decomposition and inactivation of heteropoly compounds, and the FT-IR and XRD spectrogram analysis of the catalyst obtained after the final roasting shows that the catalyst can maintain a very stable heteropoly structure, and meanwhile, the BET nitrogen adsorption and desorption analysis shows that the catalyst has a good pore channel structure and a higher specific surface area.
2) The catalyst of the invention is adopted, and the methacrolein is subjected to oxidation reaction in the presence of mixed gas of oxygen and nitrogen and water to generate methacrylic acid. The catalyst of the invention maintains higher single pass yield of methacrylic acid for a long time under higher load, the conversion rate of the methacrylic aldehyde can reach more than 70%, and the selectivity of the methacrylic acid can reach more than 84%.
3) The preparation method of the catalyst is simple and easy to carry out, and is suitable for large-scale production and application.
Drawings
FIG. 1 is a FT-IR spectrum of a calcined catalyst according to an embodiment of the invention;
figure 2 is an XRD pattern for a calcined catalyst in accordance with one embodiment of the invention.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
The performance of the invention is measured according to the following method:
The method for measuring the specific surface area and the aperture adopts a Tristar physical adsorption instrument for measurement. Before the sample is tested, heating, vacuumizing and degassing are needed. The porosity was measured on the samples at 77K, the specific surface area was calculated by the Brunauer-Emmett-Teller (BET) method, and the pore size distribution and pore volume were calculated from isothermal adsorption branches using the Barrettner-Joyner-Halenda (BJH) model.
The X-ray diffraction measurement in the invention uses an XRD powder tester produced by Bruker D4 Germany, and the test condition is 40kV and 40mV.
Fourier transform infrared (FT-IR) spectroscopy in the present invention uses Nicolet Fourier spectrophotometry manufactured in the united states.
In the invention, gas chromatography is adopted to carry out on-line analysis on the product gas, and the conversion rate of the methacrolein, the selectivity of the methacrylic acid and the single pass yield are used as evaluation catalyst performance indexes, and are defined as follows:
Methacrolein conversion (%) = (moles of methacrolein reacted/moles of methacrolein fed) ×100%
Methacrylic acid selectivity (%) = (moles of methacrylic acid produced/moles of methacrolein reacted) ×100%
Methacrylic acid single pass yield (%) = (moles of methacrylic acid produced/moles of methacrolein feed) ×100%.
The percentages and concentrations in the examples and comparative examples are by weight, unless otherwise specified.
[ Example 1]
(1) Preparation of the catalyst
9.1G H 3PMo12O40 of the solution is dissolved in deionized water, heated, refluxed and stirred at 80 ℃, then 0.25g of VOSO 4 is added after the dissolution, and the heating, refluxing and stirring are continued for 30min to obtain a solution I. 0.12g of cetyltrimethylammonium bromide was dissolved in deionized water, stirred slowly at 180rpm, 6mL of ethyl orthosilicate was added slowly dropwise at a rate of 2mL/min, and then 0.5mol/L of aqueous ammonia was added to adjust the pH to about 8 to obtain solution II. Solution I was added to solution II and heating was continued at 100 ℃ for 3h, and the solvent was evaporated by rotary evaporation. Roasting the obtained powder for 2 hours at 400 ℃ in a high-purity nitrogen atmosphere, and roasting the obtained powder for 30 minutes at a temperature rising rate of 10 ℃/min to 300 ℃ in an air atmosphere to obtain the final porous heteropolyacid catalyst, wherein the specific surface area of the catalyst can reach 108m 2/g and the aperture is about 6 nm.
The analysis of the catalyst obtained by the method through infrared spectrum shows that four main characteristic peaks exist in the catalyst within the interval of 500-1200 cm -1, which correspond to the following steps: 1066cm -1 is a central P-O bond, 966cm -1 is a terminal Mo=O t bond, 867cm -1 and 804cm -1 are intra-group Mo-O b -Mo bridge oxygen bonds and inter-group Mo-O c -Mo bridge oxygen bonds respectively, which indicates that the catalyst still maintains a stable Keggin heteropolyacid structure after the roasting method of the catalyst is disclosed in the patent (see figure 1).
Analysis of the catalyst powder by X-ray diffraction shows that diffraction peaks of the catalyst at a plurality of positions such as 2θ=10.5°, 14.9 °, 21.2 ° and 26.0 ° completely correspond to heteropolyacid H 3PMo12O14 (XRD database number 43-0314) with a Keggin structure, and further shows that the catalyst maintains a stable heteropolyacid structure after the roasting method is disclosed in the patent (see figure 2).
(2) Oxidation of methacrolein
The reactor is a phi 38 mm fluidized bed reactor: the reaction tube was filled with 3.0g of the catalyst obtained in the above step, and oxidation reaction conditions for producing methacrylic acid were: methacrolein, oxygen and nitrogen are mixed together in a ratio of water vapor=1:2.5:12:8 (molar ratio), the space velocity is 800h -1, the reaction temperature is 295 ℃, the conversion rate of methacrolein can reach more than 70%, and the selectivity of methacrylic acid can reach more than 84%. Wherein, the reaction time is 3 hours, the conversion rate of the methacrolein is 75.6%, the selectivity of the methacrylic acid is 86.8%, the conversion rate is 75.0% after the reaction time is 800 hours, and the selectivity is 86.2% after the analysis of sampling again.
Example 2
(1) Preparation of the catalyst
9.1G H 3PMo12O40 of the solution is dissolved in deionized water, heated, refluxed and stirred at 80 ℃, then 0.50g of VOSO 4 is added after the dissolution, and the heating, refluxing and stirring are continued for 30min to obtain a solution I. 0.24g of cetyltrimethylammonium bromide was dissolved in deionized water, stirred slowly at 180rpm, 10mL of ethyl orthosilicate was added slowly dropwise at a rate of 2mL/min, and then 0.5mol/L of aqueous ammonia was added to adjust the pH to about 8 to obtain solution II. Solution I was added to solution II and heating was continued at 100 ℃ for 3h, and the solvent was evaporated by rotary evaporation. The finally obtained powder is roasted for 2 hours at 400 ℃ in a high-purity nitrogen atmosphere, then is roasted for 40 minutes at a heating rate of 10 ℃/min to 300 ℃ in an air atmosphere, and the final porous heteropolyacid catalyst is obtained, and the specific surface area of the catalyst can reach 95m 2/g and the aperture is about 7.5nm through measurement.
The analysis of the catalyst obtained by the method through infrared spectrum shows that four main characteristic peaks exist in the catalyst within the interval of 500-1200 cm -1, which correspond to the following steps: 1067cm -1 is a central P-O bond, 964cm -1 is a terminal Mo=O t bond, 866cm -1 and 802cm -1 are intra-group Mo-O b -Mo bridge oxygen bonds and inter-group Mo-O c -Mo bridge oxygen bonds respectively, which indicates that the catalyst still maintains a stable Keggin heteropolyacid structure after the roasting method of the catalyst.
Analysis of the catalyst powder by X-ray diffraction shows that diffraction peaks of the catalyst at a plurality of positions such as 2θ=10.6°, 14.8 °, 21.4 ° and 26.0 ° completely correspond to heteropolyacid H 3PMo12O14 (XRD database numbering) with a Keggin structure, and further shows that the catalyst maintains a stable heteropolyacid structure after the roasting method is adopted in the patent.
(2) Oxidation of methacrolein
The reactor is a phi 38 mm fluidized bed reactor: the reaction tube was filled with 3.0g of the catalyst obtained in the above step, and oxidation reaction conditions for producing methacrylic acid were: methacrolein-oxygen-nitrogen-steam=1:2.5:12:8, space velocity 800h -1, reaction temperature 295 ℃, reaction time of 3h, sampling after reaction, methacrolein conversion of 75.6%, methacrylic acid selectivity of 86.8%, sampling again after 800h reaction for analysis, conversion of 75.0%, and selectivity of 86.2%.
Comparative example 1
(1) Preparation of the catalyst
9.1G H 3PMo12O40 of the solution is dissolved in deionized water, heated, refluxed and stirred at 80 ℃, then 0.25g of VOSO 4 is added after the dissolution, and the heating, refluxing and stirring are continued for 30min to obtain a solution I. 0.12g of cetyltrimethylammonium bromide was dissolved in deionized water, stirred slowly at 180rpm, 6mL of ethyl orthosilicate was added slowly dropwise at a rate of 2mL/min, and then 0.5mol/L of aqueous ammonia was added to adjust the pH to about 8 to obtain solution II. Solution I was added to solution II and heating was continued at 100 ℃ for 3h, and the solvent was evaporated by rotary evaporation. And finally, roasting the obtained powder to 400 ℃ at a heating rate of 5 ℃/min under the direct air atmosphere for 30min to obtain the final porous heteropolyacid catalyst, wherein the specific surface area of the catalyst is measured to be 32m 2/g, the pore diameter is about 23nm, and the distribution is uneven. The catalyst is characterized by infrared spectrum and X-ray diffraction, no obvious characteristic peak of heteropolyacid is found, which indicates that the catalyst is directly roasted in air, which can lead to the destruction of the heteropolyacid structure.
(2) Oxidation of methacrolein
The reactor is a phi 38 mm fluidized bed reactor: the reaction tube was filled with 3.0g of the catalyst obtained in the above step, and oxidation reaction conditions for producing methacrylic acid were: methacrolein-oxygen-nitrogen-steam=1:2.5:12:8, space velocity 800h -1, reaction temperature 295 ℃, sampling after 3h reaction, methacrolein conversion rate only 50.2%, methacrylic acid selectivity 60.8%, sampling again after 800h reaction analysis, conversion rate 42.6%, selectivity 49.2%.
Claims (9)
1. A porous heteropolyacid catalyst comprising a heteropolyacid and a support, the active elements of the heteropolyacid comprising Mo, V and P, the support comprising a silica-based porous support; the porous heteropolyacid catalyst is obtained by assembling an organic template agent and a precursor of silicon dioxide under an alkaline condition, mixing and drying the porous heteropolyacid catalyst with the precursor of the heteropolyacid, and then performing first roasting in an inert gas atmosphere and second roasting in an oxygen-containing atmosphere;
The specific surface area of the porous heteropolyacid catalyst is 80-120 m 2/g, and the average pore diameter is 3-8 nm;
The organic template agent comprises amphiphilic alkyl chain quaternary ammonium salt or polyether amphiphilic block copolymer;
the mass ratio of the organic template agent to the carrier is 0.005-0.05, and the mass ratio of the heteropoly acid to the carrier is 0.1-1.0;
the temperature of the first roasting is 250-450 ℃;
The second roasting temperature is 180-600 ℃;
The second calcination is performed rapidly in an oxygen-containing atmosphere.
2. The porous heteropolyacid catalyst according to claim 1, wherein the precursor of the element Mo comprises H 3PMo12O40 or H 4PMo11VO40 and/or the precursor of the element V comprises one or several of vanadyl sulfate, vanadyl oxalate, vanadyl acetylacetonate, V 2O5 or vanadyl nitrate.
3. The porous heteropolyacid catalyst according to claim 1 or 2, wherein the precursor of silica comprises one or more of silicate, silicate ester, organosilane.
4. A process for the preparation of a porous heteropolyacid catalyst according to any one of claims 1 to 3, which comprises assembling an organic template with a precursor of silica under alkaline conditions and further mixing and drying with a precursor of a heteropolyacid, followed by a first calcination in an inert gas atmosphere and a second calcination in an oxygen-containing atmosphere.
5. The method for preparing a porous heteropolyacid catalyst according to claim 4, wherein the inert gas for the first calcination comprises nitrogen, argon or helium; and/or
The temperature rising rate of the first roasting is 5 ℃/min, and the roasting time is 1-5 h.
6. The method for preparing a porous heteropolyacid catalyst according to claim 5, wherein the inert gas for the first calcination comprises nitrogen, argon or helium having a purity of 99.99% or more.
7. The method for preparing a porous heteropolyacid catalyst according to any one of claims 4 to 6, wherein the second firing temperature rise rate is 10 ℃/min and the firing time is 20 to 60min.
8. Use of a porous heteropolyacid catalyst according to any one of claims 1 to 3 in the selective oxidation of methacrolein to produce methacrylic acid.
9. The use according to claim 8, comprising the oxidation of methacrolein in the presence of a mixture of oxygen and nitrogen and water in the presence of the porous heteropoly acid catalyst to form methacrylic acid.
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