CN112705233A - Vanadium phosphorus oxygen catalyst and preparation method and application thereof - Google Patents
Vanadium phosphorus oxygen catalyst and preparation method and application thereof Download PDFInfo
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- CN112705233A CN112705233A CN201911018473.3A CN201911018473A CN112705233A CN 112705233 A CN112705233 A CN 112705233A CN 201911018473 A CN201911018473 A CN 201911018473A CN 112705233 A CN112705233 A CN 112705233A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 152
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 71
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 67
- 239000011574 phosphorus Substances 0.000 claims abstract description 67
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims description 79
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 46
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000001994 activation Methods 0.000 claims description 34
- 230000004913 activation Effects 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 229910019142 PO4 Inorganic materials 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 27
- -1 alkyl phosphate Chemical compound 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 26
- 239000011261 inert gas Substances 0.000 claims description 26
- 239000010452 phosphate Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 23
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 22
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 22
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 229910001882 dioxygen Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids 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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 description 53
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 28
- 238000001914 filtration Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000012018 catalyst precursor Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying 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
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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 discloses a vanadium phosphorus oxygen catalyst and a preparation method and application thereof. The ratio of the surface phosphorus/vanadium molar ratio A of the catalyst to the overall phosphorus/vanadium molar ratio B of the catalyst is more than or equal to 1.7. The vanadium phosphorus oxide of the invention has better catalytic activity, maleic anhydride selectivity and reaction stability.
Description
Technical Field
The invention belongs to the field of preparation of maleic anhydride, and particularly relates to a vanadium-phosphorus-oxygen catalyst, and a preparation method and application thereof.
Background
Vanadium-containing oxides are often used to select catalysts for oxidation reactions due to their good catalytic properties for oxidation reduction reactions. Among them, Vanadium Phosphorus Oxide (VPO) catalysts have been the most effective catalysts for the selective oxidation of hydrocarbons in the gas phase, especially n-butane, to maleic anhydride.
VPO catalysts can be prepared by aqueous or organic solvent processes, and early studies have generally employed pentavalent vanadium oxides such as vanadium (V) pentoxide2O5) The VPO catalyst precursor is prepared mainly by an organic method in recent research, and the preparation of the VPO catalyst precursor is generally realized by refluxing pentavalent vanadium oxide and phosphoric acid in an organic solvent to obtain the precursor. Numerous studies have demonstrated that the main phase composition of the active VPO catalyst precursor is VOHPO4·0.5H2O。
The VPO catalyst precursor described above generally needs to be activated by calcination to obtain an active catalyst that can be used for selective oxidation. During the activation process, the main phase structure of the VPO catalyst precursor is formed by VOHPO4·0.5H2O is converted to the final active phase. Meanwhile, the VPO catalyst after activation often has different crystal phase structure compositions according to the difference of the activation methods, and researchers believe that the effective crystal phase of the VPO catalyst for the reaction of preparing maleic anhydride by oxidizing n-butane is (VO)2P2O7In this crystal phase, the element V is generally considered to be represented as V4+Status. However, containing only V4+The catalyst(s) is not necessarily the best choice for catalyzing the reaction, and more research suggests that the appropriate ratio of V5+/V4+Composition, with optimal catalytic performance for the reaction.
CN1068053A discloses a method for converting a phosphorus mixed oxide catalyst precursor into an active catalyst for preparing maleic anhydride, wherein the VPO catalyst is activated by a three-stage activation method, and the active catalyst is obtained by performing activation treatment in stages in a mixed atmosphere of air, steam and inert gas.
CN1353627A discloses a phosphorus mixed oxide catalyst precursor, which is introduced into a catalyst by a polyol, aiming at controlling the carbon content in the catalyst, and the change of the carbon content determines the content of residual organic matters in the catalyst, and finally determines the structure and catalytic activity of the catalyst.
Both of the above two ways can affect the V of the final catalyst to some extent5+/V4+The composition ratio, thereby affecting the catalytic performance of the catalyst. It has been shown that the VPO catalyst has surface vanadium valences that differ from the bulk phase in comparison to the phosphorus vanadium, while having the greatest effect on its performance, and still its surface properties. When the above control measures are fixed, the performance of the catalyst is determined.
CN1075712A discloses a method for improving the performance of vanadium-phosphorus-oxygen catalyst, wherein a method for improving the stability of catalyst during use is disclosed, that is, a certain amount of trimethyl phosphate is added into the reaction gas, which is to supplement phosphorus as much as possible during the use of catalyst to maintain the stability of catalyst, but has no influence on the activation preparation and initial activity selectivity performance of catalyst.
Therefore, a method for improving the performance of the VPO catalyst is found, the stability and the selectivity of the catalyst are improved, the activity of the catalyst can meet the requirement, and the method is one of the directions for further improving the performance of the VPO catalyst. If the ratio of phosphorus to vanadium on the surface of the catalyst can be effectively increased under the condition of keeping the ratio of phosphorus to vanadium in the catalyst body unchanged, the problem is favorably solved.
Disclosure of Invention
The invention aims to solve the technical problem that the activity, stability and selectivity of the existing vanadium phosphorus oxide catalyst cannot be considered at the same time, and provides a vanadium phosphorus oxide catalyst and a preparation method and application thereof.
The inventor of the invention discovers through experiments and researches that the final performance of the catalyst can be greatly influenced by the precursor property of the catalyst when the catalyst is activated in multiple stages in mixed atmosphere, and the finally obtained catalyst is difficult to take the activity, the selectivity and the stability into consideration. Large number of research tablesIn addition, when the VPO catalyst catalyzes and selects the oxidation reaction, the stability of the surface V valence state has an important influence on the stability of the VPO catalyst, while P is important for the stabilization of the surface V valence state of the catalyst, and the surface of the catalyst has a certain tendency of removing P along with the reaction, and the stability of the catalyst is greatly influenced along with the reduction of the surface P/V ratio. On the other hand, V is often present in the catalyst activated in mixed atmosphere for improving the selectivity of the catalyst5+The higher ratio tends to seriously affect the stability of the catalyst, whereas increasing the P/V ratio of the catalyst charge significantly reduces the catalyst activity, thus creating a contradiction. The vanadium phosphorus oxygen catalyst of the invention has better selectivity and stability while ensuring the activity of catalyzing the selective oxidation of low-carbon alkane to prepare anhydride, and is particularly suitable for preparing maleic anhydride by the selective oxidation of n-butane.
To this end, a first aspect of the invention provides a vanadium phosphorus oxygen catalyst having a surface phosphorus/vanadium molar ratio A to an overall phosphorus/vanadium molar ratio B of the catalyst of ≥ 1.7.
In the present invention, the term "surface phosphorus/vanadium molar ratio" refers to the molar ratio of phosphorus element to vanadium element at the surface of the catalyst.
In the present invention, the term "overall phosphorus/vanadium molar ratio" refers to the molar ratio of all phosphorus elements to vanadium elements contained in the catalyst.
According to some embodiments of the vanadium phosphorus oxide catalyst of the present invention, the ratio of a to B is from 1.7 to 2, preferably from 1.75 to 1.85. In the present invention, the surface phosphorus/vanadium molar ratio of the catalyst and the overall phosphorus/vanadium molar ratio of the catalyst were characterized by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma emission spectrometer (ICP).
According to some embodiments of the vanadium phosphorus oxide catalyst of the present invention, the vanadium phosphorus oxide catalyst comprises a vanadium element, a phosphorus element, an oxygen element, and optionally a promoter element M, having the formula: VPxMyOz, wherein x is 1-2, preferably 1-1.5; y is 0 to 0.3, preferably 0.001 to 0.3; z is the amount of oxygen required to satisfy the elemental composition.
According to some embodiments of the vanadium phosphorus oxygen catalyst of the present invention, the promoter element M is selected from at least one of the group IIIA, IVA, VA, IVB, VB, VIB and the rare earth elements. More preferably, the promoter element M is selected from at least one of molybdenum, tungsten, niobium, boron, silicon, antimony, bismuth, zirconium and cerium. Further preferably at least one selected from molybdenum, tungsten and niobium.
According to some embodiments of the vanadium phosphorus oxide catalyst of the present invention, the vanadium phosphorus oxide catalyst has a specific surface area of 5 to 100m2A/g, preferably from 15 to 50m2(ii) in terms of/g. In the present invention, the specific surface area of the vanadium phosphorus oxygen catalyst is determined by the low temperature nitrogen adsorption BET method.
The second aspect of the invention provides a preparation method of a vanadium phosphorus oxide catalyst, which comprises the following steps:
(1) mixing and refluxing a solvent I, a vanadium-containing compound, phosphoric acid and an optional compound containing a promoter element, and carrying out first separation and first drying to obtain a solid precursor;
(2) mixing the solid precursor with a solvent II containing alkyl phosphate, and carrying out second separation and second drying to obtain an intermediate;
(3) the intermediate is activated in an atmosphere containing a phosphorus-containing organic compound.
The inventor of the invention discovers that the phosphorus is unstable when the phosphorus is supplemented in the production, but the phosphorus-containing organic compound is introduced in the step (2) of mixing the solid precursor with the solvent II containing the alkyl phosphate and the step (3) of activating, namely the phosphorus is added in the preparation process, particularly in the form of the alkyl phosphate, so that the initial activity can be maintained, and the selectivity and the stability of the maleic anhydride can be remarkably improved.
According to some embodiments of the process of the present invention, the vanadium-containing compound, phosphoric acid, the promoter element-containing compound, the alkyl phosphate-containing solvent II and the phosphorus-containing organic compound-containing atmosphere are used in amounts such that in the prepared vanadium phosphorus oxygen catalyst, a vanadium element, a phosphorus element, an oxygen element and optionally a promoter element M are comprised, which has the formula: VPxMyOz, wherein x is 1-2, preferably 1-1.5; y is 0 to 0.3, preferably 0.001 to 0.3; z is the amount of oxygen required to satisfy the elemental composition.
According to some embodiments of the methods of the present invention, the concentration of phosphoric acid is 85 to 105 wt%, the concentration being in terms of equivalent H3PO4And (4) calculating.
According to some embodiments of the method of the present invention, the feeding molar ratio of the vanadium-containing compound to the phosphoric acid is 1.05 to 1.5, wherein the vanadium-containing compound is calculated as vanadium element and the phosphoric acid is calculated as phosphorus element.
According to some embodiments of the method of the present invention, the solvent I is selected from at least one of a monohydric alcohol, a polyhydric alcohol, and an organic acid; preferably, the solvent I is selected from at least one of monohydric alcohols; more preferably, the solvent I is isobutanol and/or benzyl alcohol; more preferably, the solvent I is isobutanol and benzyl alcohol. In the present invention, the amount of solvent I to be charged is in a wide range, so as to be able to sufficiently dissolve the vanadium-containing compound, phosphoric acid, and optionally the compound containing the promoter element and perform the reduction reaction.
According to some embodiments of the method of the present invention, the vanadium-containing compound is selected from a tetravalent vanadium compound and/or a pentavalent vanadium compound; preferably at least one selected from the group consisting of ammonium metavanadate, vanadium pentoxide and vanadyl oxalate.
According to some embodiments of the method of the present invention, the promoter element is selected from at least one of group IIIA, IVA, VA, IVB, VB, VIB and rare earth elements; more preferably, the promoter element M is selected from at least one of molybdenum, tungsten, niobium, boron, silicon, antimony, bismuth, zirconium and cerium; further preferably at least one selected from molybdenum, tungsten and niobium.
According to some embodiments of the method of the present invention, the compound comprising a promoter element is selected from the group consisting of oxides, salts, or complexes corresponding to the promoter element. Preferably, the compound containing a promoter element is selected from at least one of phosphomolybdic acid, phosphotungstic acid, and niobium oxalate.
According to some embodiments of the process of the present invention, the solvent II further comprises a monohydric alcohol and/or a polyhydric alcohol, further preferably the solvent II further comprises at least one of n-butanol, sec-butanol, ethylene glycol, glycerol, 1, 4-butanediol, and pentaerythritol.
According to some embodiments of the process of the present invention, the content of alkyl phosphate in solvent II is not more than 10 wt.%, preferably 5-10 wt.%. Such as 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, and any value therebetween.
According to an embodiment of the method of the present invention, in step (1), the mixing and refluxing of the solvent I, the vanadium-containing compound, the phosphoric acid, and optionally the compound containing the promoter element may include: mixing and refluxing a solvent I, a vanadium-containing compound, phosphoric acid and an optional compound containing a promoter element. Namely a method of feeding materials in one pot. Wherein the refluxing time is 2-24 h.
According to another embodiment of the method of the present invention, in step (1), the mixing and refluxing of the solvent I, the vanadium-containing compound, the phosphoric acid, and optionally the compound containing the promoter element may further comprise: mixing and first refluxing a solvent I, a vanadium-containing compound, and optionally a compound containing a promoter element, then mixing with phosphoric acid, and performing a second refluxing. Preferably, the time of the first reflux is 1 to 4 hours, preferably 2 to 3 hours. Preferably, the time of the second reflux is 8 to 24 hours, preferably 10 to 20 hours.
According to some embodiments of the method of the present invention, preferably, the washing is performed between the first separation and the first drying, preferably, with isobutanol. The resulting filter cake is then subjected to a first drying treatment.
According to some embodiments of the method of the present invention, the conditions of the first drying and the second drying each independently comprise: the temperature is 70-150 deg.C, preferably 80-120 deg.C, and the time is 2-24 hr, preferably 4-20 hr. In the present invention, the equipment for the first drying and the second drying may be a drying oven conventional in the art, and vacuum drying is preferred.
According to some embodiments of the method of the present invention, the step of activating of step (3) comprises:
s1) carrying out first activation on the intermediate in an atmosphere I to obtain a first activated product, wherein the atmosphere I contains molecular oxygen I and optional inert gas I, carbon oxide I and water vapor I;
s2) carrying out second activation on the first activation product in an atmosphere II to obtain a second activation product, wherein the atmosphere II contains molecular oxygen II, inert gas II, carbon oxide II, water vapor II and alkyl phosphate I;
s3) carrying out third activation on the second activation product in an atmosphere III to obtain a third activation product, wherein the atmosphere III contains molecular oxygen III, inert gas III, carbon oxide III, water vapor III and alkyl phosphate II;
s4) subjecting the third activation product to a fourth activation in an atmosphere IV, wherein the atmosphere IV contains inert gas IV, water vapor IV and alkyl phosphate ester III, and optionally carbon oxide IV.
According to some embodiments of the process of the present invention, in atmosphere I, the content of molecular oxygen gas I is from 1 to 100% by weight, preferably from 5 to 80% by weight, based on the total weight of atmosphere I; the content of inert gas I is 0 to 95% by weight, preferably 20 to 80% by weight; the content of carbon oxides I is from 0 to 20% by weight, preferably from 0 to 10% by weight; the content of water vapor I is 0 to 80% by weight, preferably 0 to 50% by weight.
According to some embodiments of the method of the present invention, the content of alkyl phosphate I in atmosphere II is from 10 to 500 ppm; preferably, in the atmosphere II, the content of the molecular oxygen gas II is 5 to 80 wt%, preferably 10 to 60 wt%, based on the total weight of the atmosphere II; the content of inert gas II is 5 to 60% by weight, preferably 10 to 50% by weight; the content of carbon oxides II is from 1 to 30% by weight, preferably from 5 to 20% by weight; the content of water vapor II is 5 to 80% by weight, preferably 10 to 60% by weight.
According to some embodiments of the method of the present invention, the alkyl phosphate II is present in the atmosphere III in an amount of from 10 to 500 ppm; preferably, in atmosphere III, the content of molecular oxygen gas III is 2 to 70 wt%, preferably 4 to 50 wt%, based on the total weight of atmosphere III; the content of inert gas III is 5 to 80% by weight, preferably 20 to 50% by weight; the content of carbon oxides III is from 1 to 30% by weight, preferably from 5 to 20% by weight; the content of water vapor III is 5 to 80% by weight, preferably 10 to 70% by weight.
According to some embodiments of the method of the present invention, the content of alkyl phosphate III in atmosphere IV is from 10 to 500 ppm; preferably, the content of inert gas IV in atmosphere IV is from 10 to 80% by weight, preferably from 30 to 70% by weight, based on the total weight of atmosphere IV; the content of water vapor IV is 10 to 80% by weight, preferably 15 to 60% by weight; the content of carbon oxides IV is from 0 to 30% by weight, preferably from 1 to 15% by weight.
According to some embodiments of the method of the present invention, the molecular oxygen gas I, molecular oxygen gas II, and molecular oxygen gas III are each independently selected from air and/or oxygen.
According to some embodiments of the method of the present invention, the inert gas I, the inert gas II, the inert gas III and the inert gas IV are each independently selected from at least one of nitrogen, helium and argon.
According to some embodiments of the process of the present invention, the carbon oxide I, carbon oxide II, carbon oxide III and carbon oxide IV are each independently selected from carbon dioxide and/or carbon monoxide, preferably carbon dioxide.
According to some embodiments of the method of the present invention, the alkyl phosphate I, alkyl phosphate II and alkyl phosphate III are each independently selected from at least one of trimethyl phosphate, triethyl phosphate, dimethyl phosphate and diethyl phosphate, preferably trimethyl phosphate.
According to some embodiments of the method of the invention, the first activation conditions comprise: heating from room temperature to 280 ℃ at the heating rate of 1-20 ℃/min, and keeping the temperature for 1-6h after heating.
According to some embodiments of the method of the invention, the second activation conditions comprise: heating to the temperature of 300 ℃ and 380 ℃, wherein the heating rate is 1-10 ℃/min, and keeping the temperature for 0.5-6h after heating to the temperature.
According to some embodiments of the method of the invention, the third activation conditions comprise: heating to 390 ℃ and 430 ℃, wherein the heating rate is 1-10 ℃/min, and keeping the temperature for 0.5-6h after heating to the temperature.
According to some embodiments of the method of the present invention, the fourth activation conditions comprise: the temperature is raised to 440 ℃ and 550 ℃, the heating rate is 0.5-5 ℃/min, and the temperature is raised to 2-24 h.
In a third aspect the present invention provides a vanadium phosphorus oxide catalyst prepared by the above process.
According to some embodiments of the vanadium phosphorus oxide catalyst of the present invention, the ratio of the surface phosphorus/vanadium molar ratio A of the catalyst to the overall phosphorus/vanadium molar ratio B of the catalyst is at least 1.7. Preferably, the ratio of A to B is from 1.7 to 2, preferably from 1.75 to 1.85.
According to some embodiments of the vanadium phosphorus oxide catalyst of the present invention, the vanadium phosphorus oxide catalyst comprises a vanadium element, a phosphorus element, an oxygen element, and optionally a promoter element M, having the formula: VPxMyOz, wherein x is 1-2, preferably 1-1.5; y is 0 to 0.3, preferably 0.001 to 0.3; z is the amount of oxygen required to satisfy the elemental composition.
According to some embodiments of the vanadium phosphorus oxygen catalyst of the present invention, the promoter element M is selected from at least one of the group IIIA, IVA, VA, IVB, VB, VIB and the rare earth elements. More preferably, the promoter element M is selected from at least one of molybdenum, tungsten, niobium, boron, silicon, antimony, bismuth, zirconium and cerium. Further preferably at least one selected from molybdenum, tungsten and niobium.
According to some embodiments of the vanadium phosphorus oxide catalyst of the present invention, the vanadium phosphorus oxide catalyst has a specific surface area of 5 to 100m2A/g, preferably from 15 to 50m2/g。
In a fourth aspect the present invention provides the use of a vanadium phosphorus oxide catalyst as described above and/or a vanadium phosphorus oxide catalyst prepared according to the process described above in the preparation of maleic anhydride. For example in the preparation of maleic anhydride.
The reported activation of vanadium phosphorus oxide catalyst precursor usually adopts multi-stage heating and reaction atmosphere control method to obtain optimum catalyst. The prior proposals generally employ a molecular oxygen-containing gas such as air, an inert gas such as nitrogen and water vapor as the activated mixed atmosphere. In order to obtain a catalyst with optimal performance, it is often necessary to control the phosphorus to vanadium ratio of the catalyst, and when the phosphorus to vanadium ratio of the catalyst bulk is too high, the activity and selectivity of the catalyst can be significantly affected, and therefore, the bulk phosphorus to vanadium ratio of the vanadium phosphorus oxide catalyst is often controlled to be greater than 1 and not greater than too much, such as between 1 and 1.2. In this case, in order to improve the catalyst selectivity, it is often necessary to control the composition of the atmosphere and the temperature changes during the activation, in which case the resulting catalyst often has V5+High content and poor stability. The conventional preparation method can obtain a catalyst with enriched phosphorus surface, the ratio of the surface phosphorus/vanadium molar ratio to the total phosphorus/vanadium molar ratio (A/B) of the catalyst can reach 1.1-1.5, and the improvement of the invention can further improve the surface phosphorus-vanadium ratio of the catalyst, because the increased phosphorus is mostly distributed on the surface of the catalyst, the influence on the activity of the catalyst can be reduced to the greatest extent, and the selectivity and the stability of the catalyst can be obviously improved.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The test method and the equipment used in the test are as follows:
(1) the surface phosphorus/vanadium molar ratio and the overall phosphorus/vanadium molar ratio were determined by XPS (from Kratos, model. AXIS Ultra DLD) and ICP-AES (from Varian, model. Varian 725 ES).
(2) The BET specific surface area is measured by a low-temperature nitrogen adsorption method.
(3) The calculation formulas of the conversion rate and the selectivity in the embodiment of the invention are as follows:
n-butane conversion ═ n-butane moles reacted/n-butane feed moles x 100%,
maleic anhydride selectivity ═ mole of maleic anhydride generated/mole of n-butane reacted) × 100%.
[ example 1 ]
(1) Adding 25g of vanadium pentoxide and 0.5g of phosphomolybdic acid into a mixed solution of 250ml of isobutanol and 50ml of benzyl alcohol, heating the mixed solution under a stirring state until the mixed solution flows back, after 2 hours of backflow, adding 103.5 wt% of phosphoric acid (the metered molar ratio of phosphorus to vanadium is 1.1) into the mixed solution, heating the mixed solution, continuing to flow back for 20 hours, filtering the mixed solution after stopping heating, washing with isobutanol, and drying the obtained filter cake at 110 ℃ for 20 hours to obtain a solid precursor;
(2) heating the solid precursor in ethylene glycol/triethyl phosphate (95%/5% by weight) to 70 ℃, stirring for 1h, filtering, and drying at 110 ℃ for 4h to obtain an intermediate;
(3) heating the intermediate in an air atmosphere, raising the temperature from room temperature to 260 ℃ at a temperature raising rate of 15 ℃/min, keeping the temperature for 2h, then raising the temperature to 360 ℃ at a temperature raising rate of 3 ℃/min in an atmosphere of 35% air/10% nitrogen/5% carbon dioxide/50% steam by volume and adding 50ppm trimethyl phosphate, roasting, keeping the temperature for 2h, raising the temperature to 420 ℃ at a temperature raising rate of 2 ℃/min in a mixed atmosphere of 25% air/20% nitrogen/5% carbon dioxide/50% steam by volume and adding 50ppm trimethyl phosphate, keeping the temperature for 2h, finally raising the temperature to 480 ℃ at a temperature raising rate of 2 ℃/min in an atmosphere of 50% nitrogen/50% steam and adding 50ppm trimethyl phosphate, keeping the temperature for 4h, and obtaining the vanadium-phosphorus oxygen catalyst, wherein the chemical composition except for O (oxygen element) is as follows: VP1.18Mo0.005。
The resulting catalyst was characterized by a surface phosphorus/vanadium molar ratio A and an overall phosphorus/vanadium molar ratio B of the catalyst, the ratio of A to B being 1.75. And the specific surface area of the catalyst was measured to be 33.2m2/g。
The catalyst obtained was charged in 1.8% by volume of n-butane for 2200h-1The conversion of n-butane was 82.1 mole% and the selectivity of maleic anhydride was 71.1 mole% after the catalyst was determined to be stable, evaluated at 405 ℃ in a fixed bed reactor at space velocity. N-butane after 1000h of reaction of the catalyst under these conditionsThe conversion was 82.5 mole% and the maleic anhydride selectivity was 70.8 mole%.
[ COMPARATIVE EXAMPLE 1 ]
(1) Adding 25g of vanadium pentoxide and 0.5g of phosphomolybdic acid into a mixed solution of 250ml of isobutanol and 50ml of benzyl alcohol, heating the mixed solution under a stirring state until the mixed solution flows back, after 2 hours of backflow, adding 103.5 wt% of phosphoric acid (the metered molar ratio of phosphorus to vanadium is 1.1) into the mixed solution, heating the mixed solution, continuing to flow back for 20 hours, filtering the mixed solution after stopping heating, washing with isobutanol, and drying the obtained filter cake at 110 ℃ for 20 hours to obtain a solid precursor;
(2) heating the solid precursor in an air atmosphere, heating the solid precursor from room temperature to 260 ℃ at a heating rate of 15 ℃/min, keeping the temperature for 2h, then heating the solid precursor to 360 ℃ at a heating rate of 3 ℃/min in an atmosphere of 35% air/10% nitrogen/5% carbon dioxide/50% water vapor in a volume ratio and adding 50ppm trimethyl phosphate, roasting, keeping the temperature for 2h, then heating the solid precursor to 420 ℃ at a heating rate of 2 ℃/min in a mixed atmosphere of 25% air/20% nitrogen/5% carbon dioxide/50% water vapor in a volume ratio and adding 50ppm trimethyl phosphate, keeping the temperature for 2h, and finally heating the solid precursor to 480 ℃ at a heating rate of 2 ℃/min in an atmosphere of 50% nitrogen/50% water vapor in 50ppm trimethyl phosphate, keeping the temperature for 4h to obtain the vanadium-phosphorus oxide catalyst.
The resulting catalyst was characterized by a surface phosphorus/vanadium molar ratio A and an overall phosphorus/vanadium molar ratio B of the catalyst, the ratio of A to B being 1.32.
The catalyst obtained was charged in 1.8% by volume of n-butane for 2200h-1The conversion of n-butane was 84.1 mole% and the selectivity of maleic anhydride was 64.5 mole% after the catalyst was determined to be stable, evaluated at 405 ℃ in a fixed bed reactor at space velocity. After the catalyst is reacted for 1000 hours under the conditions, the conversion rate of normal butane is 85.3 mol percent, and the selectivity of maleic anhydride is 63.0 mol percent.
[ COMPARATIVE EXAMPLE 2 ]
(1) Adding 25g of vanadium pentoxide and 0.5g of phosphomolybdic acid into a mixed solution of 250ml of isobutanol and 50ml of benzyl alcohol, heating the mixed solution under a stirring state until the mixed solution flows back, after 2 hours of backflow, adding 103.5 wt% of phosphoric acid (the metered molar ratio of phosphorus to vanadium is 1.1) into the mixed solution, heating the mixed solution, continuing to flow back for 20 hours, filtering the mixed solution after stopping heating, washing with isobutanol, and drying the obtained filter cake at 110 ℃ for 20 hours to obtain a solid precursor;
(2) heating the solid precursor in ethylene glycol/triethyl phosphate (95%/5% by weight) to 70 ℃, stirring for 1h, filtering, and drying at 110 ℃ for 4h to obtain an intermediate;
(3) heating the intermediate in an air atmosphere, raising the temperature from room temperature to 260 ℃ at a temperature raising rate of 15 ℃/min, keeping the temperature for 2h, then raising the temperature to 360 ℃ at a temperature raising rate of 3 ℃/min in an atmosphere of 35% air/10% nitrogen/5% carbon dioxide/50% water vapor in a volume ratio, roasting, keeping the temperature for 2h, then raising the temperature to 420 ℃ at a temperature raising rate of 2 ℃/min in a mixed atmosphere of 25% air/20% nitrogen/5% carbon dioxide/50% water vapor in a volume ratio of 2 ℃/min, keeping the temperature for 2h, and finally raising the temperature to 480 ℃ at a temperature raising rate of 2 ℃/min in a 50% nitrogen/50% water vapor atmosphere, keeping the temperature for 4h to obtain the vanadium-phosphorus oxygen catalyst.
The resulting catalyst was characterized by a surface phosphorus/vanadium molar ratio A and an overall phosphorus/vanadium molar ratio B of the catalyst, the ratio of A to B being 1.6.
The catalyst obtained was charged in 1.8% by volume of n-butane for 2200h-1The conversion of n-butane was 82.7 mole% and the selectivity of maleic anhydride was 67.5 mole% after the catalyst was determined to be stable, evaluated at 405 ℃ in a fixed bed reactor at space velocity. After the catalyst is reacted for 1000 hours under the conditions, the conversion rate of the normal butane is 85.2 mol percent, and the selectivity of the maleic anhydride is 61.6 mol percent.
[ COMPARATIVE EXAMPLE 3 ]
(1) Adding 25g of vanadium pentoxide and 0.5g of phosphomolybdic acid into a mixed solution of 250ml of isobutanol and 50ml of benzyl alcohol, heating the mixed solution under a stirring state until the mixed solution flows back, after 2 hours of backflow, adding 103.5 wt% of phosphoric acid (the metered molar ratio of phosphorus to vanadium is 1.1) into the mixed solution, heating the mixed solution, continuing to flow back for 20 hours, filtering the mixed solution after stopping heating, washing with isobutanol, and drying the obtained filter cake at 110 ℃ for 20 hours to obtain a solid precursor;
(2) heating the solid precursor in ethylene glycol to 70 ℃, stirring for 1h, filtering, and drying at 110 ℃ for 4h to obtain an intermediate;
(3) heating the intermediate in an air atmosphere, raising the temperature from room temperature to 260 ℃ at a temperature raising rate of 15 ℃/min, keeping the temperature for 2h, then raising the temperature to 360 ℃ at a temperature raising rate of 3 ℃/min in an atmosphere of 35% air/10% nitrogen/5% carbon dioxide/50% water vapor in a volume ratio and adding 50ppm trimethyl phosphate, roasting, keeping the temperature for 2h, raising the temperature to 420 ℃ at a temperature raising rate of 2 ℃/min in a mixed atmosphere of 25% air/20% nitrogen/5% carbon dioxide/50% water vapor in a volume ratio and adding 50ppm trimethyl phosphate, keeping the temperature for 2h, and finally raising the temperature to 480 ℃ at a temperature raising rate of 2 ℃/min in an atmosphere of 50% nitrogen/50% water vapor in 50ppm trimethyl phosphate, keeping the temperature for 4h to obtain the vanadium-phosphorus oxide catalyst.
The resulting catalyst was characterized by a surface phosphorus/vanadium molar ratio A and an overall phosphorus/vanadium molar ratio B of the catalyst, the ratio of A to B being 1.47.
The catalyst obtained was charged in 1.8% by volume of n-butane for 2200h-1The conversion of n-butane was 83.8 mole% and the selectivity of maleic anhydride was 65.5 mole% after the catalyst was found to be stable, evaluated at 405 ℃ in a fixed bed reactor at space velocity.
[ example 2 ]
(1) Adding 25g of vanadium pentoxide and 2g of phosphomolybdic acid into a mixed solution of 250ml of isobutanol and 50ml of benzyl alcohol, heating the mixed solution under a stirring state until the mixed solution flows back, after the mixed solution flows back for 3 hours, adding 103.5 wt% of phosphoric acid (the metered molar ratio of phosphorus to vanadium is 1.1) into the mixed solution, heating the mixed solution, continuing to flow back for 10 hours, filtering the mixed solution after heating is stopped, washing the mixed solution with isobutanol, and drying the obtained filter cake at 110 ℃ for 20 hours to obtain a solid precursor;
(2) heating the solid precursor in ethylene glycol/triethyl phosphate (90%/10% by weight) to 70 ℃, stirring for 1h, filtering, and drying at 110 ℃ for 4h to obtain an intermediate;
(3) heating the intermediate in air atmosphere, raising the temperature from room temperature to 260 ℃ at a temperature raising rate of 15 ℃/min, keeping the temperature for 2h, then raising the temperature to 360 ℃ at a temperature raising rate of 3 ℃/min in an atmosphere of 45% air/5% carbon dioxide/50% water vapor by volume and adding 20ppm trimethyl phosphate, roasting, keeping the temperature for 2h, and then raising the temperature to 25% air/20% nitrogen/5% dimethyl phosphate by volumeAdding carbon oxide/50% water vapor into a mixed atmosphere of 20ppm trimethyl phosphate, raising the temperature to 420 ℃ at a heating rate of 2 ℃/min, preserving the temperature for 2h, finally raising the temperature to 480 ℃ at a heating rate of 2 ℃/min in an atmosphere of 50% nitrogen/50% water vapor and adding 20ppm trimethyl phosphate, preserving the temperature for 4h, and obtaining the vanadium-phosphorus-oxygen catalyst, wherein the chemical composition except O comprises: VP1.24Mo0.012。
The resulting catalyst was characterized by a surface phosphorus/vanadium molar ratio A and an overall phosphorus/vanadium molar ratio B of the catalyst, the ratio of A to B being 1.83. And the specific surface area of the catalyst was measured to be 31.4m2/g。
The catalyst obtained was charged in 1.8% by volume of n-butane for 2200h-1The conversion of n-butane was 81.4 mole% and the selectivity of maleic anhydride was 70.5 mole% after the catalyst was found to be stable, evaluated at 405 ℃ in a fixed bed reactor at space velocity.
[ example 3 ]
(1) Adding 25g of vanadium pentoxide and 2g of phosphomolybdic acid into a mixed solution of 250ml of isobutanol and 50ml of benzyl alcohol, heating the mixed solution under a stirring state until the mixed solution flows back, after the mixed solution flows back for 2 hours, adding 103.5 wt% of phosphoric acid (the metered molar ratio of phosphorus to vanadium is 1.1) into the mixed solution, heating the mixed solution, continuing to flow back for 12 hours, filtering the mixed solution after heating is stopped, washing the mixed solution with isobutanol, and drying the obtained filter cake at 110 ℃ for 20 hours to obtain a solid precursor;
(2) heating the solid precursor in ethylene glycol/triethyl phosphate (95%/5% by weight) to 70 ℃, stirring for 1h, filtering, and drying at 110 ℃ for 4h to obtain an intermediate;
(3) heating the intermediate in an air atmosphere, raising the temperature from room temperature to 270 ℃ at a temperature raising rate of 10 ℃/min, keeping the temperature for 2h, then raising the temperature to 350 ℃ at a temperature raising rate of 3 ℃/min in an atmosphere of 35% air/10% nitrogen/5% carbon dioxide/50% water vapor by volume and adding 25ppm trimethyl phosphate, roasting, keeping the temperature for 2h, then raising the temperature to 420 ℃ at a temperature raising rate of 2 ℃/min in a mixed atmosphere of 30% air/10% nitrogen/10% carbon dioxide/50% water vapor by volume and adding 25ppm trimethyl phosphate, keeping the temperature for 2h, and finally raising the temperature to 2 ℃ at a temperature raising rate of 2 ℃/min in an atmosphere of 50% nitrogen/50% water vapor and adding 25ppm trimethyl phosphateHeating up to 450 ℃ at a heating rate of/min and preserving heat for 6h to obtain the vanadium phosphorus oxide catalyst, wherein the chemical composition except O comprises: VP1.18Mo0.011。
The resulting catalyst was characterized by a surface phosphorus/vanadium molar ratio A and an overall phosphorus/vanadium molar ratio B of the catalyst, the ratio of A to B being 1.76. And the specific surface area of the catalyst was measured to be 32.0m2/g。
The catalyst obtained was charged in 1.8% by volume of n-butane for 2200h-1The conversion of n-butane was 82.2 mole% and the selectivity of maleic anhydride was 70.9 mole% after the catalyst was found to be stable, evaluated at 405 ℃ in a fixed bed reactor at space velocity.
[ example 4 ]
(1) Adding 25g of vanadium pentoxide and 0.65g of phosphotungstic acid into a mixed solution of 400ml of isobutanol and 50ml of benzyl alcohol, heating the mixed solution under a stirring state until the mixed solution flows back, after the mixed solution flows back for 2 hours, adding 103.5 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is 1.1) into the mixed solution, heating the mixed solution, continuing flowing back for 20 hours, filtering the mixed solution after heating is stopped, washing the mixed solution with isobutanol, and drying the obtained filter cake at 110 ℃ for 20 hours to obtain a solid precursor;
(2) heating the solid precursor in 1, 4-butanediol/triethyl phosphate (weight ratio 95%/5%) to 70 ℃, stirring for 1h, filtering, and drying at 110 ℃ for 4h to obtain an intermediate;
(3) heating the intermediate in an air atmosphere, raising the temperature from room temperature to 270 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 2h, then raising the temperature to 360 ℃ at a heating rate of 3 ℃/min in an atmosphere of 50% air/20% nitrogen/5% carbon dioxide/25% water vapor by volume ratio and adding 50ppm diethyl phosphate, roasting, keeping the temperature for 2h, then raising the temperature to 420 ℃ at a heating rate of 2 ℃/min in a mixed atmosphere of 50% air/20% nitrogen/5% carbon dioxide/25% water vapor by volume ratio and adding 50ppm diethyl phosphate, keeping the temperature for 2h, finally raising the temperature to 480 ℃ at a heating rate of 2 ℃/min in an atmosphere of 50% nitrogen/50% water vapor and adding 50ppm diethyl phosphate, keeping the temperature for 6h, and obtaining the vanadium-phosphorus-oxygen catalyst, wherein the chemical composition except for O is as follows: VP1.22W0.007。
Characterizing the resulting catalystSurface phosphorus/vanadium molar ratio a and overall phosphorus/vanadium molar ratio B of the catalyst, the ratio of a to B being 1.78. And the specific surface area of the catalyst was measured to be 29.6m2/g。
The catalyst obtained was charged in 1.8% by volume of n-butane for 2200h-1The conversion of n-butane was 80.5 mole% and the selectivity of maleic anhydride was 69.8 mole% after the catalyst was determined to be stable, evaluated at 405 ℃ in a fixed bed reactor at space velocity.
[ example 5 ]
(1) Adding 25g of vanadium pentoxide and 3g of niobium oxalate into a mixed solution of 250ml of isobutanol and 50ml of benzyl alcohol, heating the mixed solution under a stirring state until the mixed solution flows back, after 2 hours of backflow, adding 103.5 wt% of phosphoric acid (the molar ratio of phosphorus to vanadium is 1.1), heating the mixed solution, continuing to flow back for 20 hours, filtering the mixed solution after stopping heating, washing with isobutanol, and drying the obtained filter cake at 110 ℃ for 20 hours to obtain a solid precursor;
(2) heating the solid precursor in ethylene glycol/triethyl phosphate (95%/5% by weight) to 70 ℃, stirring for 1h, filtering, and drying at 110 ℃ for 4h to obtain an intermediate;
(3) heating the intermediate in an air atmosphere, raising the temperature from room temperature to 260 ℃ at a heating rate of 10 ℃/min, preserving the heat for 2h, then raising the temperature to 360 ℃ at a heating rate of 3 ℃/min in an atmosphere of 35% air/10% nitrogen/5% carbon dioxide/50% steam by volume and adding 50ppm trimethyl phosphate, roasting, preserving the heat for 2h, raising the temperature to 420 ℃ at a heating rate of 2 ℃/min in a mixed atmosphere of 25% air/20% nitrogen/5% carbon dioxide/50% steam by volume and adding 50ppm trimethyl phosphate, preserving the heat for 2h, finally raising the temperature to 480 ℃ at a heating rate of 2 ℃/min in an atmosphere of 50% nitrogen/50% steam and adding 50ppm trimethyl phosphate, preserving the heat for 4h, and obtaining the vanadium-phosphorus oxygen catalyst, wherein the chemical composition except for O is as follows: VP1.16Nb0.015。
The resulting catalyst was characterized by a surface phosphorus/vanadium molar ratio a and an overall phosphorus/vanadium molar ratio B of the catalyst, the ratio of a to B being 1.72. And the specific surface area of the catalyst was measured to be 28.7m2/g。
The catalyst was obtained in 1.8 volumesVolume% butane feed, 2200h-1The conversion of n-butane was 82.8 mole% and the selectivity of maleic anhydride was 70.9 mole% after the catalyst was determined to be stable, evaluated at 405 ℃ in a fixed bed reactor at space velocity.
The vanadium phosphorus oxide catalyst has better selectivity and stability while ensuring the activity of catalyzing the selective oxidation of the low-carbon alkane to prepare the anhydride, and is particularly suitable for preparing the maleic anhydride by the selective oxidation of the normal butane.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A vanadium phosphorus oxygen catalyst having a ratio of surface phosphorus/vanadium molar ratio A to overall phosphorus/vanadium molar ratio B of the catalyst of greater than or equal to 1.7.
2. The vanadium phosphorus oxide catalyst according to claim 1, characterized in that the ratio of a to B is from 1.7 to 2, preferably from 1.75 to 1.85.
3. The vanadium phosphorus oxide catalyst according to claim 1 or 2, characterized in that it comprises a vanadium element, a phosphorus element, an oxygen element and optionally a promoter element M, of formula: VPxMyOz, wherein x is 1-2, preferably 1-1.5; y is 0 to 0.3, preferably 0.001 to 0.3; z is the amount of oxygen required to satisfy the elemental composition;
preferably, the promoter element M is selected from at least one of the group IIIA, IVA, VA, IVB, VB, VIB and rare earth elements;
more preferably, the promoter element M is selected from at least one of molybdenum, tungsten, niobium, boron, silicon, antimony, bismuth, zirconium and cerium; further preferably at least one selected from molybdenum, tungsten and niobium.
4. The vanadium phosphorus oxide catalyst according to any one of claims 1 to 3, wherein the specific surface area of the vanadium phosphorus oxide catalyst is from 5 to 100m2A/g, preferably from 15 to 50m2/g。
5. A method for preparing a vanadium phosphorus oxide catalyst, comprising:
(1) mixing and refluxing a solvent I, a vanadium-containing compound, phosphoric acid and an optional compound containing a promoter element, and carrying out first separation and first drying to obtain a solid precursor;
(2) mixing the solid precursor with a solvent II containing alkyl phosphate, and carrying out second separation and second drying to obtain an intermediate;
(3) the intermediate is activated in an atmosphere containing a phosphorus-containing organic compound.
6. The process according to claim 5, wherein the vanadium-containing compound, phosphoric acid, the compound containing a promoter element, the solvent II containing an alkyl phosphate and the atmosphere containing a phosphorus-containing organic compound are used in amounts such that in the prepared vanadium phosphorus oxygen catalyst, a vanadium element, a phosphorus element, an oxygen element and optionally a promoter element M are contained, which has the chemical formula: VPxMyOz, wherein x is 1-2, preferably 1-1.5; y is 0 to 0.3, preferably 0.001 to 0.3; z is the amount of oxygen required to satisfy the elemental composition;
preferably, the feeding molar ratio of the vanadium-containing compound to the phosphoric acid is 1.05-1.5, wherein the vanadium-containing compound is calculated by vanadium element, and the phosphoric acid is calculated by phosphorus element.
7. The method according to claim 5 or 6, wherein the solvent I is selected from at least one of monohydric alcohol, polyhydric alcohol and organic acid; preferably, the solvent I is selected from at least one of monohydric alcohols; more preferably, the solvent I is isobutanol and/or benzyl alcohol; more preferably, the solvent I is isobutanol and benzyl alcohol;
preferably, the vanadium-containing compound is selected from at least one of ammonium metavanadate, vanadium pentoxide and vanadyl oxalate;
preferably, the promoter element is selected from at least one of group IIIA, IVA, VA, IVB, VB, VIB and rare earth elements; more preferably, the promoter element M is selected from at least one of molybdenum, tungsten, niobium, boron, silicon, antimony, bismuth, zirconium and cerium; further preferably at least one selected from molybdenum, tungsten and niobium;
preferably, the compound containing a promoter element is selected from at least one of phosphomolybdic acid, phosphotungstic acid and niobium oxalate;
preferably, the solvent II further comprises monohydric alcohol and/or polyhydric alcohol, and further preferably, the solvent II further comprises at least one of n-butyl alcohol, sec-butyl alcohol, ethylene glycol, glycerol, 1, 4-butanediol and pentaerythritol; further preferably, the content of the alkyl phosphate in the solvent II is not more than 10% by weight, preferably 5 to 10% by weight.
8. The method of claims 5-7, wherein the step of activating of step (3) comprises:
s1) carrying out first activation on the intermediate in an atmosphere I to obtain a first activated product, wherein the atmosphere I contains molecular oxygen I and optional inert gas I, carbon oxide I and water vapor I;
s2) carrying out second activation on the first activation product in an atmosphere II to obtain a second activation product, wherein the atmosphere II contains molecular oxygen II, inert gas II, carbon oxide II, water vapor II and alkyl phosphate I;
s3) carrying out third activation on the second activation product in an atmosphere III to obtain a third activation product, wherein the atmosphere III contains molecular oxygen III, inert gas III, carbon oxide III, water vapor III and alkyl phosphate II;
s4) subjecting the third activation product to a fourth activation in an atmosphere IV, wherein the atmosphere IV contains an inert gas IV, water vapor IV and alkyl phosphate ester III, and optionally carbon oxides IV;
preferably, in the atmosphere I, the content of the molecular oxygen gas I is 1-100 wt%, preferably 5-80 wt% based on the total weight of the atmosphere I; the content of inert gas I is 0 to 95% by weight, preferably 20 to 80% by weight; the content of carbon oxides I is from 0 to 20% by weight, preferably from 0 to 10% by weight; the content of water vapor I is 0 to 80% by weight, preferably 0 to 50% by weight;
preferably, in atmosphere II, the content of alkyl phosphate I is between 10 and 500 ppm; preferably, in the atmosphere II, the content of the molecular oxygen gas II is 5 to 80 wt%, preferably 10 to 60 wt%, based on the total weight of the atmosphere II; the content of inert gas II is 5 to 60% by weight, preferably 10 to 50% by weight; the content of carbon oxides II is from 1 to 30% by weight, preferably from 5 to 20% by weight; the content of water vapor II is 5 to 80% by weight, preferably 10 to 60% by weight;
preferably, in atmosphere III, the content of alkyl phosphate II is between 10 and 500 ppm; preferably, in atmosphere III, the content of molecular oxygen gas III is 2 to 70 wt%, preferably 4 to 50 wt%, based on the total weight of atmosphere III; the content of inert gas III is 5 to 80% by weight, preferably 20 to 50% by weight; the content of carbon oxides III is from 1 to 30% by weight, preferably from 5 to 20% by weight; the content of water vapor III is 5 to 80% by weight, preferably 10 to 70% by weight;
preferably, the content of alkyl phosphate III in the atmosphere IV is 10-500 ppm; preferably, the content of inert gas IV in atmosphere IV is from 10 to 80% by weight, preferably from 30 to 70% by weight, based on the total weight of atmosphere IV; the content of water vapor IV is 10 to 80% by weight, preferably 15 to 60% by weight; the content of carbon oxides IV is from 0 to 30% by weight, preferably from 1 to 15% by weight;
preferably, the molecular oxygen gas I, molecular oxygen gas II and molecular oxygen gas III are each independently selected from air and/or oxygen;
preferably, the inert gas I, the inert gas II, the inert gas III and the inert gas IV are each independently selected from at least one of nitrogen, helium and argon;
preferably, the carbon oxides I, II, III and IV are each independently selected from carbon dioxide and/or carbon monoxide, preferably carbon dioxide;
preferably, the alkyl phosphate I, the alkyl phosphate II and the alkyl phosphate III are each independently selected from at least one of trimethyl phosphate, triethyl phosphate, dimethyl phosphate and diethyl phosphate, preferably trimethyl phosphate;
preferably, the conditions of the first activation include: heating from room temperature to 280 ℃, wherein the heating rate is 1-20 ℃/min, and keeping the temperature for 1-6h after heating;
preferably, the second activation conditions include: heating to the temperature of 300 ℃ and 380 ℃, wherein the heating rate is 1-10 ℃/min, and keeping the temperature for 0.5-6h after heating to the temperature;
preferably, the third activation conditions include: heating to 390 ℃ and 430 ℃, wherein the heating rate is 1-10 ℃/min, and keeping the temperature for 0.5-6h after heating to the temperature;
preferably, the fourth activation conditions include: the temperature is raised to 440 ℃ and 550 ℃, the heating rate is 0.5-5 ℃/min, and the temperature is raised to 2-24 h.
9. A vanadium phosphorus oxide catalyst prepared by the process of any one of claims 5 to 8.
10. Use of a vanadium phosphorus oxide catalyst as claimed in any one of claims 1 to 4 and 9 and/or a vanadium phosphorus oxide catalyst prepared by a process as claimed in any one of claims 5 to 8 in the preparation of maleic anhydride.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068053A (en) * | 1991-06-27 | 1993-01-20 | 孟山都公司 | Vanadium/phosphorus mixed oxide catalyst precursors is transformed into the method for active catalysts for production of maleic anhydride |
| US5185455A (en) * | 1992-02-18 | 1993-02-09 | Monsanto Company | Method for improving the performance of VPO catalysts |
| CN1471430A (en) * | 2000-10-27 | 2004-01-28 | �����ɷ� | Catalyst and method for producing maleic anhydride |
| CN101213019A (en) * | 2005-05-02 | 2008-07-02 | 伊内奥斯美国公司 | Novel phosphorus addition process for improvement of catalysts suitable for maleic anhydride production |
| CN103949277A (en) * | 2014-05-21 | 2014-07-30 | 厦门大学 | Supported vanadyl pyrophosphate catalyst prepared by selective oxidation of n-butane and preparation method thereof |
| CN107866240A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride and preparation method thereof |
| CN107866244A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | Vanadium phosphorus catalyst and preparation method thereof |
| CN109053647A (en) * | 2018-08-23 | 2018-12-21 | 常州新日催化剂有限公司 | A kind of production technology of preparing cis-anhydride by n-butane oxidation |
-
2019
- 2019-10-24 CN CN201911018473.3A patent/CN112705233A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068053A (en) * | 1991-06-27 | 1993-01-20 | 孟山都公司 | Vanadium/phosphorus mixed oxide catalyst precursors is transformed into the method for active catalysts for production of maleic anhydride |
| US5185455A (en) * | 1992-02-18 | 1993-02-09 | Monsanto Company | Method for improving the performance of VPO catalysts |
| CN1075712A (en) * | 1992-02-18 | 1993-09-01 | 孟山都公司 | Improve the method for vanadium-phosphorus-performance of VPO catalysts |
| CN1471430A (en) * | 2000-10-27 | 2004-01-28 | �����ɷ� | Catalyst and method for producing maleic anhydride |
| CN101213019A (en) * | 2005-05-02 | 2008-07-02 | 伊内奥斯美国公司 | Novel phosphorus addition process for improvement of catalysts suitable for maleic anhydride production |
| CN103949277A (en) * | 2014-05-21 | 2014-07-30 | 厦门大学 | Supported vanadyl pyrophosphate catalyst prepared by selective oxidation of n-butane and preparation method thereof |
| CN107866240A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst for preparing maleic anhydride and preparation method thereof |
| CN107866244A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | Vanadium phosphorus catalyst and preparation method thereof |
| CN109053647A (en) * | 2018-08-23 | 2018-12-21 | 常州新日催化剂有限公司 | A kind of production technology of preparing cis-anhydride by n-butane oxidation |
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