CN111229309B - Supported catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof - Google Patents
Supported catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof Download PDFInfo
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- CN111229309B CN111229309B CN201811441450.9A CN201811441450A CN111229309B CN 111229309 B CN111229309 B CN 111229309B CN 201811441450 A CN201811441450 A CN 201811441450A CN 111229309 B CN111229309 B CN 111229309B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 150000003681 vanadium Chemical class 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 150000000703 Cerium Chemical class 0.000 claims abstract description 6
- LJTKTWZETXWYSX-UHFFFAOYSA-N [O].[P].[V].[Ce] Chemical compound [O].[P].[V].[Ce] LJTKTWZETXWYSX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 76
- 238000002425 crystallisation Methods 0.000 claims description 57
- 230000008025 crystallization Effects 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 48
- 239000010936 titanium Substances 0.000 claims description 38
- 230000003301 hydrolyzing effect Effects 0.000 claims description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 36
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 36
- 229910052719 titanium Inorganic materials 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 34
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 19
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 19
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 19
- 238000000967 suction filtration Methods 0.000 claims description 19
- 239000001488 sodium phosphate Substances 0.000 claims description 17
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 17
- 235000011008 sodium phosphates Nutrition 0.000 claims description 17
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 6
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000012002 vanadium phosphate Substances 0.000 claims description 4
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 3
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 3
- WKCZSFRAGKIIKN-UHFFFAOYSA-N 2-(4-tert-butylphenyl)ethanamine Chemical compound CC(C)(C)C1=CC=C(CCN)C=C1 WKCZSFRAGKIIKN-UHFFFAOYSA-N 0.000 claims description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- LJBTWTBUIINKRU-UHFFFAOYSA-K cerium(3+);triperchlorate Chemical compound [Ce+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LJBTWTBUIINKRU-UHFFFAOYSA-K 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 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
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 53
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 51
- 229910021641 deionized water Inorganic materials 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 34
- 239000007864 aqueous solution Substances 0.000 description 34
- 229910052710 silicon Inorganic materials 0.000 description 34
- 239000010703 silicon Substances 0.000 description 34
- 238000011068 loading method Methods 0.000 description 25
- -1 polytetrafluoroethylene Polymers 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 description 17
- 239000012266 salt solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000011206 ternary composite Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SKAXWKNRKROCKK-UHFFFAOYSA-N [V].[Ce] Chemical compound [V].[Ce] SKAXWKNRKROCKK-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a supported cerium-vanadium-phosphorus-oxygen composite oxide/TS-1 (CeVPO/TS-1) catalyst for preparing maleic anhydride by oxidizing n-butane. The preparation of the catalyst is that soluble cerium salt, vanadium salt and phosphate precursor are synchronously introduced in the preparation process of the titanium-silicon molecular sieve (TS-1), thereby realizing the regulation and control of the distribution of the cerium-vanadium-phosphorus-oxygen composite oxide in the TS-1 pore channel. TS-1 not only serves as a carrier, but also is a high-efficiency oxidation catalyst, so that the carrier and the CeO are mixed 2 、V 2 O 5 And P 2 O 5 The components form a synergistic effect. The preparation method is simple to operate and easy to amplify. Can be used in the fields of preparing maleic anhydride by n-butane oxidation and the like, and has better industrial application prospect.
Description
Technical Field
The invention belongs to the field of novel catalytic material preparation, and particularly relates to a preparation method of a supported type maleic anhydride catalyst (CeVPO/TS-1) prepared by oxidizing n-butane.
Background
As an important organic chemical raw material, maleic anhydride (maleic anhydride for short, also called maleic anhydride) is the third largest organic anhydride, which is second only to phthalic anhydride and acetic anhydride. Is widely applied to the fields of petrochemical industry, food processing, medicine, building materials and the like. And can be further converted into high value-added chemicals such as 1, 4-butanediol, tetrahydrofuran, gamma-butyrolactone and the like.
The prior maleic anhydride industrial production in China mainly comprises three technical routes, namely a benzene oxidation method, an n-butane oxidation method and a carbon four-fraction (butylene) oxidation method. Among them, the benzene oxidation method is the most developed maleic anhydride preparation process, and the related reactor and catalyst are mature, but the price of the raw material benzene is relatively expensive, and the generated environmental problem is serious. Subsequently, the U.S. petroleum-texas chemical company developed a process for producing maleic anhydride by oxidizing butene in 1960. In 1974, monsanto, USA, successfully developed a production process for preparing maleic anhydride by oxidizing n-butane, wherein n-butane is cheaper as a raw material. The process has the advantages of low raw material price, small environmental pollution and the like, and the process gradually replaces the first two preparation processes at present and becomes a main route for producing maleic anhydride. The vanadium phosphorus oxide catalyst is the most effective catalyst of the route, and the optimization improvement of the vanadium phosphorus oxide catalyst has never been stopped since the commercialization thereof was realized. In order to further improve the activity and selectivity of the vanadium phosphorus oxide catalyst and improve the economic benefit of the existing device, a lot of optimization and improvement works are carried out by a plurality of research institutions.
Currently, VPO catalysts produced commercially are all unsupported catalysts. The VPO catalyst has small specific surface area, low mechanical strength and poor heat transfer effect. Therefore, research and search have been conducted on the supported VPO catalyst. Patent CN1935374 provides a method for preparing a supported VPO catalyst, using phosphoric acid treated ZrO 2 The catalyst is a carrier, and although the performance of the catalyst is partially improved, the selectivity of the maleic anhydride is obviously reduced. Patent CN106140125 also provides a preparation method of a supported catalyst for preparing maleic anhydride by n-butane oxidation. Using monodisperse SiO 2 The microspheres are used as carriers, a large amount of organic alcohol is used as a solvent and a reducing agent, the preparation route is complicated, large-scale preparation is difficult to realize, and further industrial application of the microspheres is limited.
As described above, most of the conventional catalysts for producing maleic anhydride by n-butane oxidation are non-supported catalysts. The specific surface area and the mechanical strength of the catalyst cannot be effectively improved on the premise that the catalytic performance is not affected. Aiming at the problems, the invention develops a preparation method of a supported CeVPO/TS-1 catalyst. In the preparation process of the titanium-silicon molecular sieve (TS-1), soluble cerium salt, vanadium salt and phosphate precursor are synchronously introduced, so that the uniform distribution of the ternary composite oxide on the surface of the TS-1 is realized. TS-1 not only acts as a carrier, but also is a highly efficient oxidation catalyst, thereby forming a synergistic effect with the active components. The preparation method is simple to operate and easy to amplify.
Disclosure of Invention
The invention aims to provide a preparation method of a supported catalyst for preparing maleic anhydride by n-butane oxidation, which can effectively regulate and control the distribution state of a ternary composite oxide on the surface of a TS-1 carrier.
The invention provides a preparation method of a supported CeVPO/TS-1 catalyst, which is characterized by comprising the following steps of: firstly, ethyl orthosilicate and tetraalkylammonium hydroxide are mixed according to a molar ratio of 1:0.02-0.8, hydrolyzing for 0.5-10h at 30-90 ℃ to obtain solution A;
tetrabutyl titanate and tetraalkylammonium hydroxide are mixed according to a molar ratio of 1:0.5-20, hydrolyzing for 0.5-10h at 30-90 ℃ to obtain solution B;
dropwise adding the solution B into the solution A; the molar ratio of Ti to Si is 1:20-300 parts of;
then dripping soluble cerium salt, vanadium salt and phosphoric acid (and/or phosphate) into the mixed solution under the stirring condition, and then transferring the mixed solution into a crystallization kettle for crystallization for 12-72 hours at the temperature of 50-250 ℃; after crystallization, carrying out suction filtration separation and drying; then roasting at 350-450 deg.c to obtain a series of supported CeVPO/TS-1 catalysts.
The invention provides a preparation method of a supported CeVPO/TS-1 catalyst, which is characterized by comprising the following steps of: the catalyst comprises the following components, 10-85% of titanium silicalite molecular sieve (TS-1) by mass percentage; and 2 to 10% of CeO supported thereon 2 20-50% of V 2 O 5 (ii) a And 20-50% of P 2 O 5 。
The invention provides a preparation method of a supported CeVPO/TS-1 catalyst, which is characterized by comprising the following steps of: 2-10% of CeO 2 5-50% of V 2 O 5 (ii) a And 8-50% of P 2 O 5 Is derived from a cerium vanadium phosphorus oxygen composite oxide.
The invention provides a preparation method of a supported CeVPO/TS-1 catalyst, which is characterized by comprising the following steps of: the atomic ratio of V to P is between 0.5 and 3, preferably between 1.0 and 1.5; the atomic ratio of Ce to V is 0.01 to 0.5, preferably 0.1 to 0.25.
The invention provides a preparation method of a supported CeVPO/TS-1 catalyst, which is characterized by comprising the following steps of: the active components of the cerium vanadium phosphorus oxygen composite oxide are uniformly loaded on the surface of TS-1; TS-1 not only serves as a carrier, but also is a high-efficiency oxidation catalyst, so that a synergistic effect is formed with the ternary composite oxide component.
The invention provides a preparation method of a supported CeVPO/TS-1 catalyst, which is characterized by comprising the following steps of: the tetraalkyl ammonium hydroxide comprises one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide and tetrabutyl ammonium hydroxide;
cerium salts include in particular: cerium nitrate, cerium acetate, cerium chloride, cerium ammonium nitrate, cerium perchlorate, cerium phosphate, or a mixture of one or more of the above components;
the vanadium salt specifically comprises: potassium vanadate, vanadium chloride, sodium vanadate, ammonium vanadate, vanadyl sulfate, vanadium phosphate, ammonium metavanadate, sodium metavanadate, vanadium sulfate, vanadyl oxalate, vanadyl acetylacetonate, sodium metavanadate, sodium pyrovanadate, or a mixture of one or more of the above components.
Phosphoric acid and/or phosphates include in particular: phosphoric acid, metaphosphoric acid, pyrophosphoric acid, cerium phosphate, vanadium phosphate, ammonium phosphate, sodium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, sodium metaphosphate, sodium pyrophosphate, or a mixture of one or more of the above components.
The invention provides a preparation method of a supported CeVPO/TS-1 catalyst, which can be applied to the reaction of preparing maleic anhydride by oxidizing n-butane.
Compared with the reported preparation method of the catalyst for preparing maleic anhydride by oxidizing the supported n-butane, the method has the following advantages: TS-1 is not only used as a carrier, but also is a high-efficiency oxidation catalyst, so that a synergistic effect is formed with the active component of the ternary composite oxide.
Detailed Description
Example 1:
adding 50.7mL of tetraethoxysilane and 91mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12 hours to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above is added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. The three salt solutions were added dropwise to the previously prepared mixture and stirred for 2h. And transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 61.25 percent is obtained.
Example 2: different cerium vanadium atomic ratio (Ce/V = 0.1)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 2.16g of cerium nitrate into 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 60.20 percent is obtained.
Example 3: different cerium vanadium atomic ratio (Ce/V = 0.25)
Adding 50.7mL of tetraethoxysilane and 91mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12 hours to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 5.41g of cerium nitrate into 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. The three salt solutions were added dropwise to the previously prepared mixture and stirred for 2h. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 61.6 percent is obtained.
Example 4: different vanadium phosphorus atomic ratio (V/P = 0.25)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above is added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 2.33g of ammonium metavanadate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. The three salt solutions were added dropwise to the previously prepared mixture and stirred for 2h. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 54.42 percent is obtained.
Example 5: different vanadium phosphorus atomic ratio (V/P = 3)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 28.01g of ammonium metavanadate was dissolved in 30mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 80.15 percent is obtained.
Example 6: tetraalkylammonium hydroxide species
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L tetraethylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetraethylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 61.25 percent is obtained.
Example 7: tetraalkylammonium hydroxide species
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L tetrabutylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; 2mL of tetrabutyl titanate was dissolved in 40mL0.5mol/L tetrabutylammonium hydroxide aqueous solution, and stirred at 40 ℃ for hydrolysis for 30min to obtain a titanium source precursor solution. The titanium source solution described above is added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 61.25 percent is obtained.
Example 8: kind of cerium salt
Adding 50.7mL of tetraethoxysilane and 91mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12 hours to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above is added dropwise to the previous silicon source precursor solution. 2.59g of cerium chloride was dissolved in 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting at 350 ℃ to obtain the CeVPO/TS-1 catalyst with the total loading of 61.25 percent
Example 9: kind of cerium salt
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above is added dropwise to the previous silicon source precursor solution. Dissolving 3.34g of cerium nitrate into 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting at 350 ℃ to obtain the CeVPO/TS-1 catalyst with the total loading of 61.25 percent
Example 10: vanadium salt species
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above is added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 7.84g of vanadium chloride was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting at 350 ℃ to obtain the CeVPO/TS-1 catalyst with the total loading of 61.25 percent
Example 11: vanadium salt species
Adding 50.7mL of tetraethoxysilane and 91mL0.5mol/L tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12 hours to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above is added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 12.21g of vanadyl oxalate was dissolved in 15mL of deionized water, and 13.09g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting at 350 ℃ to obtain the CeVPO/TS-1 catalyst with the total loading of 61.25 percent
Example 12: kind of phosphoric acid (salt)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 9.18g of ammonium dihydrogen phosphate was dissolved in 15mL of deionized water. The three salt solutions were added dropwise to the previously prepared mixture and stirred for 2h. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization is finished, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 61.25 percent is obtained.
Example 13: kind of phosphoric acid (salt)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above is added dropwise to the previous silicon source precursor solution. Dissolving 4.57g of cerium nitrate into 10mL of deionized water; 5.83g of ammonium metavanadate was dissolved in 15mL of deionized water, and 7.82g of phosphoric acid was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization is finished, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 61.25 percent is obtained.
Example 14: different loadings (total loading 15%)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 0.83g of cerium nitrate into 10mL of deionized water; 0.53g of ammonium metavanadate was dissolved in 15mL of deionized water, and 1.53g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 15% is obtained.
Example 15: different loadings (total loading 50%)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 7.09g of cerium nitrate into 10mL of deionized water; 3.61g of ammonium metavanadate was dissolved in 15mL of deionized water, and 6.49g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 50% is obtained.
Example 16: different loadings (total loading 70%)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 3.54g of cerium nitrate into 10mL of deionized water; 15.05g of ammonium metavanadate was dissolved in 20mL of deionized water, and 9.20g of sodium phosphate was dissolved in 15mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 70% is obtained.
Example 17: different loadings (total loading 85%)
Adding 50.7mL of ethyl orthosilicate and 91mL0.5mol/L of tetrapropylammonium hydroxide aqueous solution into a 250mL round-bottom flask, and stirring and hydrolyzing at 35 ℃ for 12h to obtain a silicon source precursor solution; dissolving 2mL of tetrabutyl titanate in 40mL0.5mol/L tetrapropylammonium hydroxide aqueous solution, and stirring and hydrolyzing at 40 ℃ for 30min to obtain a titanium source precursor solution. The titanium source solution described above was added dropwise to the previous silicon source precursor solution. Dissolving 11.80g of cerium nitrate into 10mL of deionized water; 18.05g of ammonium metavanadate was dissolved in 15mL of deionized water, and 54.09g of sodium phosphate was dissolved in 50mL of deionized water. And (3) respectively dropwise adding the three salt solutions into the mixed solution prepared previously, and continuously stirring for 2 hours. And (3) transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining for crystallization for 72 hours at the temperature of 200 ℃. After crystallization, carrying out suction filtration separation and drying. Then roasting treatment is carried out at 350 ℃, and the CeVPO/TS-1 catalyst with the total loading of 85% is obtained.
Application example
The cerium vanadium phosphorus oxide catalysts prepared in examples 1, 3, 4 and 6 were tableted to prepare 40-60 mesh samples. Normal pressure-0.6 MPa, 380-450 deg.c, n-butane mixed gas volume space velocity of 1000-3500 h-1 and butane concentration of 1.0-1.8 vol%, and the activity of the catalyst is evaluated. The composition of the reaction product was analyzed by gas chromatography.
The following table shows the corresponding reaction results of a portion of the catalysts prepared by the process of the present invention
Claims (7)
1. The application of the supported CeVPO/TS-1 catalyst in the reaction of preparing maleic anhydride by oxidizing n-butane is characterized in that: firstly, ethyl orthosilicate and tetraalkylammonium hydroxide are mixed according to a molar ratio of 1:0.02-0.8, hydrolyzing for 0.5-10h at 30-90 ℃ to obtain solution A;
tetrabutyl titanate and tetraalkylammonium hydroxide are mixed according to a molar ratio of 1:0.5-20, hydrolyzing for 0.5-10h at 30-90 ℃ to obtain solution B;
dropwise adding the solution B into the solution A; the molar ratio of Ti to Si is 1:20-300 parts of;
then dripping soluble cerium salt, vanadium salt and phosphoric acid or phosphate into the mixed solution under the stirring condition, and then transferring the mixed solution into a crystallization kettle for crystallization for 12-72 hours at the temperature of 50-250 ℃; after crystallization, carrying out suction filtration separation and drying; then roasting at 350-450 ℃ to obtain the supported CeVPO/TS-1 catalyst.
2. Use according to claim 1, characterized in that: the catalyst comprises the following components, 10-85% of titanium silicalite molecular sieve (TS-1) by mass percentage; and 2 to 10% of CeO supported thereon 2 5-50% of V 2 O 5 (ii) a And 8-50% of P 2 O 5 。
3. Use according to claim 1, characterized in that: 2-10% of CeO 2 20-50% of V 2 O 5 (ii) a And 20-50% of P 2 O 5 The three oxides are derived from cerium vanadium phosphorus oxygen composite oxides, and the mass content of the carrier is 25-55%.
4. Use according to claim 1, characterized in that: the atomic ratio of V to P is 0.5-3; the atomic ratio of Ce to V is 0.01-0.5, and the mass content of the carrier is 30-90%.
5. Use according to claim 4, characterized in that: the atomic ratio of V to P is 1.0-1.5; the atomic ratio of Ce to V is 0.1-0.25.
6. Use according to any one of claims 1 to 4, wherein: the active components of the cerium vanadium phosphorus oxygen composite oxide are uniformly loaded on the surface of TS-1; TS-1 not only serves as a carrier, but also is a high-efficiency oxidation catalyst.
7. Use according to claim 1, characterized in that: the tetraalkylammonium hydroxide comprises one or more than two of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide;
the cerium salt specifically includes: one or more of cerium nitrate, cerium acetate, cerium chloride, ammonium cerium nitrate or cerium perchlorate;
the vanadium salt specifically comprises: one or more of potassium vanadate, vanadium chloride, sodium vanadate, ammonium vanadate, vanadyl sulfate, vanadium phosphate, ammonium metavanadate, sodium metavanadate, vanadium sulfate, vanadyl oxalate, sodium metavanadate, or sodium pyrovanadate;
the phosphoric acid and/or phosphate salts include, in particular: one or more than two of phosphoric acid, metaphosphoric acid, pyrophosphoric acid, vanadium phosphate, ammonium phosphate, sodium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, sodium metaphosphate and sodium pyrophosphate.
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