CN114471644A - 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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- CN114471644A CN114471644A CN202011163252.8A CN202011163252A CN114471644A CN 114471644 A CN114471644 A CN 114471644A CN 202011163252 A CN202011163252 A CN 202011163252A CN 114471644 A CN114471644 A CN 114471644A
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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 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 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 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000002243 precursor Substances 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
- 238000001354 calcination Methods 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- -1 silicate ester Chemical class 0.000 claims description 5
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 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
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 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
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 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
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 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
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects 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
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005070 sampling Methods 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
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910017299 Mo—O Inorganic materials 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
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling 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
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 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
- 230000002468 redox effect Effects 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
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 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
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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
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- 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
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- 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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Abstract
The invention relates to a porous heteropoly acid catalyst and a preparation method thereof, wherein the porous heteropoly acid catalyst comprises heteropoly acid and a carrier, is assembled with the carrier under an alkaline condition through an organic template agent, is further mixed with the heteropoly acid and dried, and is obtained by rapidly roasting in an oxygen-containing atmosphere after roasting in an inert gas atmosphere. The porous heteropolyacid 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 a mixed gas of oxygen and nitrogen and water to generate the methacrylic acid. The catalyst of the invention maintains higher methacrylic acid one-way yield for a long time under higher load, the conversion rate of methacrolein can reach more than 70%, and the selectivity of 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
Since heteropoly compounds have both good acid sites and redox properties, they are widely used catalysts, and have been industrially used in the fields of olefin hydration, bisphenol a synthesis, methacrylic acid production by methacrolein oxidation, and the like. Most heteropoly compounds synthesized by the traditional hydrothermal method have no uniform mesoscopic pore structure and low specific surface area, so that the contact between the active sites of the heteropoly compounds 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 always a relatively troublesome problem. The conventional method for removing the template agent comprises a solvent extraction method and a roasting method, wherein the former method is to dissolve and remove the organic template agent by heating and refluxing in an organic solvent, the method is carried out at a lower temperature, the stability of the heteropoly acid structure can be ensured, but a large amount of organic solvent is needed, the production process cost is improved, and meanwhile, the structure stability of the heteropoly catalyst is maintained in the preparation process, but when the heteropoly catalyst is used in some catalytic reactions with higher temperature, the structure is easy to collapse; the latter is to remove the template agent by high-temperature roasting in an oxygen-containing atmosphere, and because the Keggin structure heteroanions of the heteropoly acid have poor thermal stability at higher temperature, the method can directly cause the collapse of the structure of the heteropolyanion to form compact oxide and also has a porous structure.
Therefore, how to ensure the thermal stability of the catalyst on the premise of ensuring the high specific surface area and the porous structure of the heteropoly compound catalyst is a relatively important research direction in the field. US4621155A proposes that the catalyst prepared by this method can improve the yield of methacrylic acid to some extent during the process of preparing methacrylic acid, but the effect is limited, by adding an organic base during the precipitation process to increase the specific surface area of the catalyst and to control the pore size distribution. 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 component is improved. US3939096A reports a catalyst using porous silica as a carrier, which has good catalytic performance for the reaction of acrolein oxidation to produce acrylic acid, but has poor catalytic performance for the reaction of methacrolein oxidation. The anion unit size of the heteropoly acid compound is large, the microporous material is used as a carrier, the loading is difficult to be carried out by utilizing the surface of an inner hole, and particularly, the blockage of the pore channel of the carrier is serious when the loading capacity is high. CN110694687A proposes a supported nano heteropolyacid catalyst taking large-aperture silicon dioxide with the aperture of 50-500 nm as a carrier, wherein the particle size of the supported active component heteropolyacid is 4-10 nm, and the supported active component heteropolyacid has high selectivity and stability in catalyzing the oxidation reaction of methylacrolein. However, the large-aperture silica carrier in the method is prepared by a polymer colloidal crystal template method, and the steps are very complicated, so that the method is not suitable for large-scale industrial production.
Disclosure of Invention
The invention aims to solve the technical problems of low specific surface area, poor thermal stability and the like of a heteropoly acid catalyst, and provides a porous heteropoly acid catalyst with high specific surface area and thermal stability, and a preparation method and application thereof. Namely, the first purpose of the invention is to provide a porous heteropolyacid catalyst, which comprises heteropolyacid and a carrier, wherein the active elements of the heteropolyacid comprise one or more of Mo, V and P, and the carrier comprises a silicon-based porous carrier;
the porous heteropoly acid catalyst is obtained by assembling an organic template agent and a carrier under an alkaline condition, further mixing and drying the organic template agent and heteropoly acid, and then roasting the mixture for two times in an inert gas atmosphere and an oxygen-containing atmosphere.
According to some embodiments of the invention, the precursor of elemental Mo comprises H3PMo12O40Or H4PMo11VO40。
According to some embodiments of the invention, the precursor of element V comprises vanadyl sulfate, vanadyl oxalate, vanadium acetylacetonate, V2O5Or one or more of 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 silicon dioxide comprises ethyl orthosilicate, methyl orthosilicate.
According to some embodiments of the invention, the organic templating agent comprises an amphiphilic alkyl chain quaternary ammonium salt or a polyether-based amphiphilic block copolymer. According to some embodiments of the invention, the organic templating agent 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 present invention, the mass of the organic templating agent and the support is 0.005 to 0.05, and according to some embodiments of the present invention, the mass of the organic templating agent and the support is 0.01 to 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 120m2(ii)/g, the average pore diameter is 3 to 8 nm.
The second purpose of the invention is to provide a preparation method of the porous heteropolyacid catalyst, which comprises the steps of mixing and drying the heteropolyacid and the carrier in the presence of the organic template agent, and then carrying out primary roasting in an inert gas atmosphere and secondary roasting in an oxygen-containing atmosphere.
According to some embodiments of the present invention, the method of mixing and drying the heteropoly acid and the support in the presence of the organic template further comprises the steps of:
(1) heating and dissolving a 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 value to be alkalescent;
(3) increasing 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) to dryness 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 stirring speed of the low-speed stirring is 120 to 180 rpm.
According to some embodiments of the invention, the speed of adding the silica precursor in the step (2) is 0.5-10 mL/min; according to some embodiments of the invention, the rate of adding the silica precursor is 2-4 mL/min.
According to some embodiments of the invention, the alkaline solution of step (2) is selected from the group consisting of aqueous ammonia, sodium hydroxide solution, potassium hydroxide solution; according to some embodiments of the present invention, the alkali solution in the step (2) is preferably ammonia.
According to some embodiments of the present invention, the stirring speed in step (3) is increased to 220-800 rpm.
According to some embodiments of the present invention, the heating reflux temperature in step (3) is 60 to 120 ℃, and the heating time is 0.5 to 2 hours.
According to some embodiments of the present invention, the rotary evaporation in step (4) is performed at a heating temperature of 80-150 ℃, a heating time of 0.5-10 hours, and a stirring speed of 220-800 rpm.
According to some embodiments of the invention, the inert gas used for the first firing comprises nitrogen, argon or helium.
According to some embodiments of the invention, the inert gas used in the first firing comprises nitrogen, argon or helium with a purity of 99.99% or more.
According to some embodiments of the invention, the temperature of the first roasting is 250-450 ℃, the heating rate is 5 ℃/min, and the roasting time is 1-5 h.
According to some embodiments of the invention, the second roasting is performed rapidly in an oxygen-containing atmosphere, the roasting temperature is 180 to 600 ℃, the heating rate is 10 ℃/min, and the roasting time is 20 to 60 min.
The invention also aims to provide the application of the porous heteropolyacid catalyst in the preparation of methacrylic acid through selective oxidation of methacrolein.
According to some embodiments of the present invention, the application includes that methacrolein is oxidized in the presence of a mixed gas of oxygen and nitrogen and water to generate methacrylic acid using the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1) the present invention was made based on the finding that the inventors propose a method of heat treatment which can be carried out by two-step calcination in order to solve the problem that the heteropolyanion structure and the channel structure of the catalyst are destroyed during the heat treatment of the porous heteropoly acid catalyst. After the dry powder is obtained through rotary evaporation, the first step is to calcine in inert gas atmosphere, the purpose is to carbonize the template agent, the obtained carbon and the silicon dioxide carrier can play a good role in stabilizing and protecting the structure and the porous framework of the heteropoly acid, and the metal oxide formed by the direct structural collapse of the heteropoly acid is avoided. And in the second step, the catalyst is quickly roasted in an oxygen-containing atmosphere, the aim is to remove the carbon obtained in the previous step and avoid the reduction of the activity of the catalyst caused by the coverage of the carbon on the surface of an active component, in the step, the residual carbon in the previous step is favorable for maintaining the stable structure of heteropoly acid, meanwhile, the decomposition and inactivation of heteropoly compounds can be avoided or reduced by quickly heating and roasting for a short time, FT-IR and XRD spectrogram analysis of the finally roasted catalyst shows that the catalyst can keep a very stable heteropoly section structure, and simultaneously, BET nitrogen adsorption and desorption analysis shows that the catalyst has a good pore structure and a higher specific surface area.
2) According to the catalyst of the present invention, methacrolein is oxidized in the presence of a mixed gas of oxygen and nitrogen and water to produce methacrylic acid. The catalyst of the invention maintains higher methacrylic acid one-way yield for a long time under higher load, the conversion rate of methacrolein can reach more than 70%, and the selectivity of 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 graph of the FT-IR spectrum of a calcined catalyst according to one embodiment of the present invention;
figure 2 is an XRD spectrum of the calcined catalyst according to one embodiment of the present invention.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The performance of the invention was determined as follows:
the method for measuring the specific surface area and the aperture adopts a Tristar physical adsorption instrument to measure. Before the sample is tested, heating, vacuumizing and degassing treatment is required. The porosity was measured at 77K for the sample and the specific surface area was calculated by the Brunauer-Emmett-Teller (BET) method, using the Barrettner-Joyner-Halenda (BJH) model, from the isothermal adsorption branch the pore size distribution and pore volume was calculated.
The X-ray diffraction in the present invention was measured using an XRD powder tester manufactured by Bruker D4 Germany under the test conditions of 40kV and 40 mV.
Fourier transform Infrared (FT-IR) spectroscopy used in the present invention is Nicolet Fourier spectrophotometry, manufactured in the United states.
In the invention, the product gas is analyzed on line by adopting a gas chromatograph, and the conversion rate of methacrolein, the selectivity of methacrylic acid and the single-pass yield are taken as indexes for evaluating the performance of the catalyst, and the indexes are defined as follows:
methacrolein conversion (%) - (moles of methacrolein reacted/moles of methacrolein feed) × 100%
Methacrylic acid selectivity (%). times.100% (moles of methacrylic acid formed/moles of methacrolein reacted)
Methacrylic acid single pass yield (%) × 100% (moles of methacrylic acid produced/moles of methacrolein fed).
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 H3PMo12O40Dissolving in deionized water, heating at 80 deg.C, refluxing, stirring, dissolving, and adding 0.25g VOSO4And continuously heating, refluxing and stirring for 30min to obtain a solution I. 0.12g of hexadecyl trimethyl ammonium bromide is dissolved in deionized water, slowly stirred at the rotating speed of 180rpm, 6mL of ethyl orthosilicate is slowly dripped at the speed of 2mL/min, and then 0.5mol/L of ammonia water is added to adjust the pH value to about 8, so that a solution II is obtained. 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 finally obtained powder at 400 ℃ for 2h in a high-purity nitrogen atmosphere, then roasting the powder at 300 ℃ at a heating rate of 10 ℃/min in an air atmosphere for 30min to obtain a final porous heteropolyacid catalyst, and determining that the specific surface area of the catalyst can reach 108m2The pore diameter is about 6 nm.
Analysis of the catalyst obtained by the method through infrared spectroscopy shows that the catalyst is 500-1200 cm-1Four main characteristic peaks exist in the interval, which respectively correspond to: 1066cm-1Is a central P-O bond of 966cm-1Is end position Mo ═ OtKey, 867cm-1And 804cm-1Are each intragroup Mo-ObOxygen bond of-Mo bridge and intergroup Mo-Oc-Mo bridging oxygen bond, indicating that the catalyst is calcined according to the patentThe Keggin heteropoly acid structure is still stable after the method (see attached figure 1).
The analysis of the catalyst powder by X-ray diffraction revealed that the diffraction peaks of the catalyst at several positions such as 2 θ ═ 10.5 °, 14.9 °, 21.2 ° and 26.0 ° and Keggin structure heteropoly acid H3PMo12O14(XRD database No. 43-0314) and further shows that the catalyst retains a stable heteropolyacid structure after the calcination process described in this patent (see FIG. 2).
(2) Oxidation reaction 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 the oxidation reaction conditions for producing methacrylic acid were: methacrolein, oxygen, nitrogen and water vapor in a molar ratio of 1:2.5:12:8 at a space velocity of 800h-1The reaction temperature is 295 ℃, the conversion rate of the methacrolein can reach more than 70%, and the selectivity of the methacrylic acid can reach more than 84%. Wherein, sampling after reaction for 3h, the conversion rate of methacrolein is 75.6%, the selectivity of methacrylic acid is 86.8%, and sampling analysis after reaction for 800h again shows that the conversion rate is 75.0%, and the selectivity is 86.2%.
Example 2
(1) Preparation of the catalyst
9.1g H3PMo12O40Dissolving in deionized water, heating at 80 deg.C, refluxing, stirring, dissolving, and adding 0.50g VOSO4And continuously heating, refluxing and stirring for 30min to obtain a solution I. 0.24g of hexadecyl trimethyl ammonium bromide is dissolved in deionized water, the mixture is slowly stirred at the rotating speed of 180rpm, 10mL of ethyl orthosilicate is slowly dripped at the speed of 2mL/min, and then 0.5mol/L of ammonia water is added to adjust the pH value to about 8, so that a solution II is obtained. Solution I was added to solution II and heating was continued at 100 ℃ for 3h, and the solvent was evaporated by rotary evaporation. Calcining the finally obtained powder at 400 ℃ for 2h in a high-purity nitrogen atmosphere, then calcining the powder at 300 ℃ at a heating rate of 10 ℃/min in an air atmosphere for 40min to obtain a final porous heteropoly acid catalyst, and determining that the specific surface area of the catalyst can reach 95m2(ii)/g, pore diameter is about 7.5 nm.
By infrared spectroscopyAnalysis of the catalyst obtained by the method shows that the catalyst is 500-1200 cm-1Four main characteristic peaks exist in the interval, which respectively correspond to: 1067cm-1Is a central P-O bond, 964cm-1Is end position Mo ═ OtKey, 866cm-1And 802cm-1Are respectively Mo-O in the groupbOxygen bond of-Mo bridge and intergroup Mo-OcMo bridge oxygen bonds, which shows that the catalyst still maintains a stable Keggin heteropoly acid structure after the roasting method of the invention.
The analysis of the catalyst powder by X-ray diffraction shows that the diffraction peaks of the catalyst at a plurality of positions such as 2 theta 10.6 degrees, 14.8 degrees, 21.4 degrees and 26.0 degrees are in contact with Keggin structure heteropoly acid H3PMo12O14(XRD database numbering) completely corresponds to each other, further showing that the catalyst maintains a stable heteropoly acid structure after the roasting method described in the patent.
(2) Oxidation reaction 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 the oxidation reaction conditions for producing methacrylic acid were: methylacrolein, oxygen, nitrogen and water vapour in the ratio of 1:2.5:12:8 at space velocity of 800 hr-1And the reaction temperature is 295 ℃, a sample is taken after 3 hours of reaction, the conversion rate of the methacrolein is 75.6 percent, the selectivity of the methacrylic acid is 86.8 percent, and the conversion rate is 75.0 percent and the selectivity is 86.2 percent after the reaction of 800 hours and the sample is taken again for analysis.
Comparative example 1
(1) Preparation of the catalyst
9.1g H3PMo12O40Dissolving in deionized water, heating at 80 deg.C, refluxing, stirring, dissolving, and adding 0.25g VOSO4And continuously heating, refluxing and stirring for 30min to obtain a solution I. 0.12g of hexadecyl trimethyl ammonium bromide is dissolved in deionized water, slowly stirred at the rotating speed of 180rpm, 6mL of ethyl orthosilicate is slowly dripped at the speed of 2mL/min, and then 0.5mol/L of ammonia water is added to adjust the pH value to about 8, so that a solution II is obtained. 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 heated up at the speed of 5 ℃/min under the direct air atmosphereRoasting at 400 deg.C for 30min to obtain final porous heteropolyacid catalyst, and determining that the specific surface area of said catalyst is 32m2(ii)/g, pore diameter of about 23nm, and uneven distribution. The catalyst is characterized by infrared spectrum and X-ray diffraction, no obvious characteristic peak of the heteropoly acid is found, and the fact that the catalyst is directly roasted in the air can cause the damage of the heteropoly acid structure.
(2) Oxidation reaction of methacrolein
The reactor is a phi 38 mm fluidized bed reactor: the oxidation reaction conditions for the preparation of methacrylic acid by filling 3.0g of the catalyst obtained in the above step into a reaction tube were as follows: methylacrolein, oxygen, nitrogen and water vapour in the ratio of 1:2.5:12:8 at space velocity of 800 hr-1When the reaction temperature is 295 ℃, a sample is taken after 3 hours of reaction, the conversion rate of the methacrolein is only 50.2 percent, the selectivity of the methacrylic acid is 60.8 percent, and the conversion rate is 42.6 percent and the selectivity is 49.2 percent after the sample is taken again for analysis after 800 hours of reaction.
Claims (11)
1. A porous heteropoly acid catalyst comprises a heteropoly acid and a carrier, wherein the active element of the heteropoly acid comprises one or more of Mo, V and P, and the carrier comprises a silicon-based porous carrier; the porous heteropoly acid catalyst is obtained by assembling an organic template agent and a carrier under an alkaline condition, further mixing and drying the organic template agent and heteropoly acid, and then roasting the mixture for two times in an inert gas atmosphere and an oxygen-containing atmosphere.
2. The porous heteropolyacid catalyst of claim 1, wherein the precursor of elemental Mo comprises H3PMo12O40Or H4PMo11VO40And/or the element V precursor comprises vanadyl sulfate, vanadyl oxalate, vanadium acetylacetonate, V2O5Or one or more of vanadyl nitrate.
3. The porous heteropolyacid catalyst of claim 1, wherein the silica-based porous support comprises one or more of silica, silica-alumina magnesia, zeolite; preferably, the precursor of the silicon dioxide comprises one or more of silicate, silicate ester and organosilane.
4. The porous heteropolyacid catalyst of claim 1, wherein the organic templating agent comprises an amphiphilic alkyl chain quaternary ammonium salt or a polyether-based amphiphilic block copolymer.
5. The porous heteropolyacid catalyst according to claim 1, wherein the mass of the organic template and the support is 0.005 to 0.05, and the mass ratio of the heteropolyacid to the support is 0.1 to 1.0.
6. The porous heteropolyacid catalyst according to claim 1, wherein the specific surface area of the porous heteropolyacid catalyst is 80 to 120m2(ii)/g, the average pore diameter is 3 to 8 nm.
7. A process for the preparation of a porous heteropolyacid catalyst as claimed in any of claims 1 to 6, which comprises drying a mixture of heteropolyacid and support in the presence of an organic template, followed by a first calcination in an inert gas atmosphere and a second calcination in an oxygen-containing atmosphere.
8. The method of preparing a porous heteropolyacid catalyst according to claim 7, wherein the inert gas for the first calcination comprises a gas selected from the group consisting of nitrogen, argon and helium, preferably nitrogen, argon and helium having a purity of 99.99% or more; and/or
The temperature of the first roasting is 250-450 ℃, the heating rate is 5 ℃/min, and the roasting time is 1-5 h.
9. The method for preparing a porous heteropolyacid catalyst according to claim 7, wherein the second calcination is carried out rapidly in an oxygen-containing atmosphere; and/or
The second roasting temperature is 180-600 ℃, the heating rate is 10 ℃/min, and the roasting time is 20-60 min.
10. Use of a porous heteropolyacid catalyst according to any of claims 1 to 6 in the selective oxidation of methacrolein to produce methacrylic acid.
11. The use according to claim 10, wherein the use comprises subjecting methacrolein to an oxidation reaction in the presence of a mixed gas of oxygen and nitrogen and water in the presence of the porous heteropolyacid catalyst to produce methacrylic acid.
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| CN115532314B (en) * | 2021-06-29 | 2024-01-05 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by methyl tertiary butyl ether and preparation method and application thereof |
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