CN107866245A - Catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof - Google Patents
Catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof Download PDFInfo
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- CN107866245A CN107866245A CN201610849412.1A CN201610849412A CN107866245A CN 107866245 A CN107866245 A CN 107866245A CN 201610849412 A CN201610849412 A CN 201610849412A CN 107866245 A CN107866245 A CN 107866245A
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- Prior art keywords
- catalyst
- anhydride
- butane oxidation
- preparing cis
- preparation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 32
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 33
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 238000005469 granulation Methods 0.000 claims description 19
- 230000003179 granulation Effects 0.000 claims description 19
- 239000001273 butane Substances 0.000 claims description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 235000021355 Stearic acid Nutrition 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 239000008117 stearic acid Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229920002472 Starch Polymers 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 239000008107 starch Substances 0.000 claims description 13
- 241000219782 Sesbania Species 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 241000220317 Rosa Species 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 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
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 235000013844 butane Nutrition 0.000 description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 24
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 150000008064 anhydrides Chemical class 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical class [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 description 1
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000008346 aqueous phase Substances 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
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
The present invention relates to a kind of catalyst of preparing cis-anhydride by n-butane oxidation.Mainly solve the problems, such as that catalytic activity is relatively low in the prior art.The present invention includes three kinds of vanadium, phosphorus, oxygen elements by using main body, is aided with a certain amount of metal promoter；According to overall catalyst weight gauge, wherein containing：V element is 26 35%, and P elements are 14 20%, and oxygen element is 30 50%；Metal promoter is 0.02 7% catalyst, and the catalyst is handled through constant temperature and humidity, repeatedly adulterates pore creating material and post forming processing, improves the catalytic performance of catalyst, improve the intensity of catalyst, can be applied to preparing cis-anhydride by n-butane oxidation field.
Description
Technical field
The present invention relates to catalyst of a kind of preparing cis-anhydride by n-butane oxidation reaction and preparation method thereof.
Background technology
Maleic anhydride, abbreviation cis-butenedioic anhydride, that is, maleic anhydride, it is a kind of conventional important Organic Chemicals, is generation
Consumption figure is only second to the third-largest acid anhydrides kind of phthalic anhydride and aceticanhydride in boundary.Cis-butenedioic anhydride is widely used in petrochemical industry, food chemistry, doctor
The industries such as medicine, construction material, it is mainly used in synthesizing unsaturated polyester resin, lube oil additive, food additives, Isosorbide-5-Nitrae-fourth two
A series of important organic chemicals and fine chemicals such as alcohol (BDO), gamma-butyrolacton (GBL), tetrahydrofuran (THF).
The early stage production of cis-butenedioic anhydride is prepared by the selective oxidation of benzene, but because benzene is to the harmfulness of human body and environment,
And the influence of economic factor, the ratio that the production technology of benzene method is shared in maleic anhydride production increasingly reduce.Due to possessing raw material
It is inexpensive, pollution is relatively light, carbon atom utilization rate is high and maleic anhydride production low cost and other advantages, preparing cis-anhydride by n-butane oxidation technology by
Gradually turn into the main route of maleic anhydride production.
At present, researcher has done numerous studies and trial to the catalyst material for preparing cis-anhydride by n-butane oxidation, it is believed that
Vanadium-phosphorus-oxygen (VPO) catalyst is still catalyst system maximally efficient so far.Preparation method on vpo catalyst has
There are substantial amounts of open source literature and patented technology, it is typically using water-soluble to summarize and be concentrated mainly on industrialized vpo catalyst
Presoma is made in agent or organic solvent method, and gained presoma obtains final catalyst by calcination activation and shaping.Due to organic
The catalyst that solvent method obtains relative to Aqueous phase has larger specific surface area, therefore has certain advantage.This method
Mainly using the single or mixed system of isobutanol and phenmethylol as solvent.Therefore, the preparation process of specific organic solvent method is
Vanadium source is dissolved in organic solvent, is stirred at reflux reaction, and adds phosphorus source, continues backflow and obtains presoma, finally heat treatment is lived
Change obtains catalyst.
Current vanadium-phosphor oxide catalyst has had a variety of structures, such as sheet, trifolium-shaped etc..But traditional prepares these
The method of catalyst configuration thing all has a problem that the lateral compressive strength of i.e. gained structure is weaker.So-called lateral resistance to compression
Intensity is to instigate structure to crush required power.Lateral compressive strength is an important indicator in catalyst manufacturing procedures.Cause
To be activated in the heat treatment of catalyst, packed and transported, install into reactor, in course of reaction, catalyst all can be by certain journey
The pressure of degree, if side loaded intensity is excessively weak, the wear rate of catalyst will be higher.So-called wear rate refers to unit mass
The quality of part is lost after catalyst experience wear.The wear rate of the weaker catalyst of side loaded intensity in above process compared with
Height, catalyst debris caused by abrasion or particle can largely increase the pressure drop of industrial reactor operating process, to life
Production adversely affects.
, typically can be by increasing the method for shaping of catalyst pressure in order to solve this weak major issue of side loaded intensity
To realize, so, the compressive strength of catalyst can be increased to a certain extent really, but briquetting pressure increase can be carried substantially
The density of high catalyst, the bulk density of catalyst is caused to improve, while specific surface area declines.The decline of specific surface area not only can
Cause the relative activity of catalyst to reduce, so as to reduce yield, can also cause reaction radiating difficult, cause reaction focus is high and ask
Topic.
Mix lubricant based on catalyst precursor and graphite is prepared the VPO of sheet by patent CN102325593A
Molded catalyst bodies.The specific pore volume PV (mL/g) of described molded catalyst bodies, the bulk density ρ (kg/ of molded catalyst bodies
L), the geometrical surface A geometry (mm of molded catalyst bodies2) and geometric volume V geometry (mm3) meet following condition：0.275 ＜
PV ρ A geometry/V geometry, the pressure loss caused by the molded catalyst bodies are relatively low.
Patent WO2010/047949A1 proposes the forming method of trifolium-shaped catalyst configuration thing, the catalyst circle
Cylinder radius and blade radius are about 6.25, and have the wear rate for being approximately less than 10% and the lateral compressive strength more than 20 pounds,
Wear rate relative to reducing about 40% in the past.
The content of the invention
One of technical problems to be solved by the invention are for catalyst configuration thing lateral compressive strength in the prior art
It is low, the problem of wear rate is high, a kind of catalyst of preparing cis-anhydride by n-butane oxidation is disclosed, employs and locates under the conditions of constant temperature and humidity
Catalyst precursor is managed, structure lateral compressive strength height is obtained under conditions of pore creating material is added and after carrying out secondary tabletting,
The low catalyst of wear rate.
The two of the technical problems to be solved by the invention are to provide a kind of with solving one of technical problem corresponding catalysis
The preparation method of agent.
The three of the technical problems to be solved by the invention are to provide a kind of with solving one of technical problem corresponding raising
The method of preparing cis-anhydride by n-butane oxidation yield.
To solve one of above-mentioned technical problem, technical scheme disclosed in this invention is：A kind of preparing cis-anhydride by n-butane oxidation
Catalyst, catalyst has rose structure；Its main body includes vanadium source compound, P source compound and oxygen source compound,
It is aided with micro metal promoter；According to total catalyst weight, wherein be 26-35%, P elements 14-20% containing v element,
Oxygen element is 30-50%；Metal promoter is 0.02-7%.
In above-mentioned technical proposal, the catalyst for preparing cis-anhydride by n-butane oxidation, it is characterised in that v element is selected from refined
At least one of rear ammonium metavanadate, vanadic anhydride or organic acid vanadium；Metal promoter is selected from cobalt, molybdenum, bismuth, sodium, zirconium at least
It is a kind of.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is used for n butane oxidation system
The preparation method of the catalyst of cis-butenedioic anhydride, key step include：Metal promoter is mixed with organic solvent first, then adds vanadium source
Compound, P source compound is added, after being heated to reflux 6-18h under continuous stirring, products therefrom filtration drying is obtained into solid
Obtained vpo catalyst precursor powder is dried, carries out being thermally treated resulting in catalyst at 300-500 DEG C.
In above-mentioned technical proposal, the particle size of vanadium source compound used is 1.5-3.5 μm.Phosphorus source compound and vanadium
P/V ratios in source compound are 0.8-1.3；Required organic solvent is the alcohols solvent with reducing power.
In above-mentioned technical proposal, the preparation method for the catalyst of preparing cis-anhydride by n-butane oxidation, it is characterised in that described
Precursor powder uniformly obtains mixture A with mix lubricant；Said mixture A is placed in constant temperature constant humidity baking oven, processing 3~
24h, thermostat temperature are 20~60 DEG C, and constant humidity humidity is relative humidity 40~95%；FYD types are used under 10~40MPa pressure
Powder compressing machine carries out a compressing tablet process, obtains one-shot forming catalyst；By above-mentioned one-shot forming catalyst breakage, sieve,
The catalyst that grain graininess is 20~160 mesh is taken, as pre-granulation particle；Above-mentioned pre-granulation particle is placed on rotary pelleting machine
Secondary compressing tablet process is carried out, obtains the hollow cylinder catalyst configuration thing that height is 4~6mm；By above-mentioned catalyst configuration thing
It is placed in 380~500 DEG C of temperature and carries out heat treatment activation with activation phenomenon；The activation phenomenon is selected from lighter hydrocarbons, air, indifferent gas
At least one of body, water vapour or carbon dioxide；Described lubricant be selected from graphite, talcum powder, stearate, its quality with
The mass ratio of precursor powder is 1~8:100.Described lubricant is preferably graphite
Constant temperature and humidity processing is carried out after pore creating material is added in above-mentioned technical proposal, in mixture A, the pore creating material is selected from hard
At least one of resin acid, soluble starch or sesbania powder.Preferable technical scheme is that pore creating material is selected from stearic acid and solubility
Starch；Preferred technical scheme is that pore creating material is selected from stearic acid, soluble starch and sesbania powder.
In above-mentioned technical proposal, added again in pre-granulation particle and carry out rotary tablet compression after pore creating material again, it is described to make
Hole agent is selected from least one of stearic acid, soluble starch or sesbania powder.Preferable technical scheme is that pore creating material is selected from tristearin
Acid and soluble starch；Preferred technical scheme is that pore creating material is selected from stearic acid, soluble starch and sesbania powder.
In above-mentioned technical proposal, the pressure limit of a compressing tablet process is 15~30MPa.
To solve the three of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind improves n butane oxidation system
The method of cis-butenedioic anhydride, using any one catalyst described in claim 1~9, it is characterised in that catalyst is with molar concentration
1-1.5%mol butane raw material reacts in fixed bed reactors, produces cis-butenedioic anhydride, its reaction process condition：Air speed be 1000~
3000hr-1, reaction temperature be 300~500 DEG C, reaction pressure is normal pressure.
Using technical scheme, catalyst precursor is handled under the conditions of constant temperature and humidity, in secondary addition pore-creating
Structure lateral compressive strength height, the low catalyst of wear rate are obtained after secondary tabletting is carried out under conditions of agent.Prepared by it
Catalyst substantially improves the catalytic performance of catalyst, and butanes conversion reaches 88%, Selectivity of maleic anhydride more than 60%, meanwhile,
The lateral compressive strength of catalyst configuration thing is more than 110N/cm, and the proportion of goods damageds are less than 8% after 600h reacts.
The present invention, but content not thereby limiting the invention are further illustrated with example below.
Embodiment
【Embodiment 1】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；By said mixture A temperature be 30 DEG C, suitable humidity be 85% constant temperature constant humidity baking oven in handle
12h；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then crushed, sieved, take 80~
The part of 140 mesh；Above-mentioned pre-granulation particle is transferred on rotary pelleting machine, catalyst configuration thing is highly 5mm, is catalyzed
Agent structure, lateral compressive strength 132N/cm, wear rate 2.3%；It is 1.5%mol's by gained catalyst and molar concentration
Butane raw material reacts, its reaction process condition：2000hr-1Check and rate, measure in fixed bed reactors under air speed, 400 DEG C of normal pressures
Butanes conversion is 81.6%, and yield of maleic anhydride 50.3%, its appraisal result refers to table 1.
【Embodiment 2】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material stearic acid 5g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is 85%
Processing 12h in constant temperature constant humidity baking oven；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then by it
It is broken, sieve, take the part of 80~140 mesh；Above-mentioned pre-granulation particle is transferred on rotary pelleting machine, catalyst configuration thing is high
Spend for 6mm, obtain catalyst configuration thing, lateral compressive strength 118N/cm, wear rate 3.6%；By gained catalyst with mole
The butane raw material that concentration is 1.5%mol reacts, its reaction process condition：2000hr-1It is anti-in fixed bed under air speed, 400 DEG C of normal pressures
Answer in device and check and rate, it is 90.3% to measure butanes conversion, and yield of maleic anhydride 58.7%, its appraisal result refers to table 1.
【Embodiment 3】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；By said mixture A temperature be 30 DEG C, suitable humidity be 85% constant temperature constant humidity baking oven in handle
12h；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then crushed, sieved, take 80~
The part of 140 mesh is as pre-granulation particle；Pore creating material stearic acid 5g will be added in above-mentioned pre-granulation particle, be transferred to rotary tablet compression
On machine, catalyst configuration thing is highly 5mm, obtains catalyst configuration thing, lateral compressive strength 102N/cm, wear rate
6.4%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, its reaction process condition：2000hr-1It is empty
Checked and rated under speed, 400 DEG C of normal pressures in fixed bed reactors, it is 89.8% to measure butanes conversion, and yield of maleic anhydride 58.4%, it is examined
Comment the results detailed in Table 1.
【Embodiment 4】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material stearic acid 2.5g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is 85%
Constant temperature constant humidity baking oven in processing 12h；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then will
It is broken, screening, takes the part of 80~140 mesh；Pore creating material stearic acid 2.5g will be added in above-mentioned pre-granulation particle again, is shifted
Onto rotary pelleting machine, catalyst configuration thing is highly 4mm, obtains catalyst configuration thing, lateral compressive strength 107N/cm,
Wear rate 3.8%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, its reaction process condition：
2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, it is 89.9% to measure butanes conversion, yield of maleic anhydride
58.6%, its appraisal result refers to table 1.
【Embodiment 5】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material soluble starch 2.5g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is
Processing 12h in 85% constant temperature constant humidity baking oven；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；So
Crushed, sieved afterwards, take the part of 80~140 mesh；Pore creating material soluble starch will be added again in above-mentioned pre-granulation particle
2.5g, it is transferred on rotary pelleting machine, catalyst configuration thing is highly 5mm, obtains catalyst configuration thing, lateral compressive strength is
116N/cm, wear rate 3.7%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, its reaction process
Condition：2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, it is 84.8% to measure butanes conversion, cis-butenedioic anhydride
Yield 55.2%, its appraisal result refer to table 1.
【Embodiment 6】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material sesbania powder 2.5g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is 85%
Constant temperature constant humidity baking oven in processing 12h；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then will
It is broken, screening, takes the part of 80~140 mesh；Pore creating material sesbania powder 2.5g will be added in above-mentioned pre-granulation particle again, is shifted
Onto rotary pelleting machine, catalyst configuration thing is highly 5mm, obtains catalyst configuration thing, lateral compressive strength 120N/cm,
Wear rate 3.5%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, its reaction process condition：
2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, it is 84.0% to measure butanes conversion, yield of maleic anhydride
54.9%, its appraisal result refers to table 1.
【Embodiment 7】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material stearic acid 2.5g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is 85%
Constant temperature constant humidity baking oven in processing 12h；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then will
It is broken, screening, takes the part of 80~140 mesh；Pore creating material soluble starch 2.5g will be added in above-mentioned pre-granulation particle again,
It is transferred on rotary pelleting machine, catalyst configuration thing is highly 5mm, obtains catalyst configuration thing, lateral compressive strength 113N/
Cm, wear rate 2.5%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, its reaction process condition：
2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, it is 89.2% to measure butanes conversion, yield of maleic anhydride
58.2%, its appraisal result refers to table 1.
【Embodiment 8】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material stearic acid 2.5g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is 85%
Constant temperature constant humidity baking oven in processing 12h；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then will
It is broken, screening, takes the part of 80~140 mesh；Pore creating material sesbania powder 2.5g will be added in above-mentioned pre-granulation particle again, is shifted
Onto rotary pelleting machine, catalyst configuration thing is highly 5mm, obtains catalyst configuration thing, lateral compressive strength 116N/cm,
Wear rate 2.4%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, its reaction process condition：
2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, it is 87.1% to measure butanes conversion, yield of maleic anhydride
54.3%, its appraisal result refers to table 1.
【Embodiment 9】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material soluble starch 2.5g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is
Processing 12h in 85% constant temperature constant humidity baking oven；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；So
Crushed, sieved afterwards, take the part of 80~140 mesh；Pore creating material stearic acid 2.5g will be added in above-mentioned pre-granulation particle again,
It is transferred on rotary pelleting machine, catalyst configuration thing is highly 5mm, obtains catalyst configuration thing, lateral compressive strength 109N/
Cm, wear rate 3.2%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, its reaction process condition：
2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, it is 87.5% to measure butanes conversion, yield of maleic anhydride
56.4%, its appraisal result refers to table 1.
【Embodiment 10】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material sesbania powder 2.5g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is 85%
Constant temperature constant humidity baking oven in processing 12h；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then will
It is broken, screening, takes the part of 80~140 mesh；Pore creating material stearic acid 2.5g will be added in above-mentioned pre-granulation particle again, is shifted
Onto rotary pelleting machine, catalyst configuration thing is highly 5mm, obtains catalyst configuration thing, lateral compressive strength 111N/cm,
Wear rate 3.0%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, its reaction process condition：
2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, it is 86.8% to measure butanes conversion, yield of maleic anhydride
54.7%, its appraisal result refers to table 1.
【Embodiment 11】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；Pore creating material stearic acid 2g will be added in said mixture A, be 30 DEG C in temperature, suitable humidity is 85%
Processing 12h in constant temperature constant humidity baking oven；Then in 20MPa pressure lower sheetings, one-shot forming catalyst configuration thing is obtained；Then by it
It is broken, sieve, take the part of 80~140 mesh；Pore creating material soluble starch 1.5g+ fields will be added in above-mentioned pre-granulation particle again
Cyanines powder 1.5g, is transferred on rotary pelleting machine, and catalyst configuration thing is highly 5mm, obtains catalyst configuration thing, lateral pressure resistance
Spend for 117N/cm, wear rate 2.1%；Gained catalyst and molar concentration are reacted for 1.5%mol butane raw material, it reacts
Process conditions：2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, it is 89.2% to measure butanes conversion,
Yield of maleic anhydride 58.8%, its appraisal result refer to table 1.
【Comparative example 1】
0.5g cobalt oxalates are mixed with 120mL phenmethylols with 360mL isobutanols, then add 50.4g vanadic anhydrides, then
65mL phosphoric acid is added, after being heated to reflux 16h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor
End, powder catalyst presoma is sieved, take 50g to be less than the presoma of 200 mesh, be sufficiently mixed with 1.5g graphite powders
Even formation mixture A；In temperature it is drying process 12h in 120 DEG C of convection oven by said mixture A；Then pressed in 20MPa
Power lower sheeting, obtain one-shot forming catalyst configuration thing；Then crushed, sieve, take the part of 80~140 mesh as pre-manufactured
Grain particle；Above-mentioned pre-granulation particle is transferred on rotary pelleting machine, catalyst configuration thing is highly 5mm, obtains catalyst structure
The divine force that created the universe, lateral compressive strength 96N/cm, wear rate 8.8%；Butane by gained catalyst with molar concentration for 1.5%mol
Raw material reacts, its reaction process condition：2000hr-1Checked and rated under air speed, 400 DEG C of normal pressures in fixed bed reactors, measure butane
Conversion ratio is 84.5%, and yield of maleic anhydride 52.3%, its appraisal result refers to table 1.
Table 1
Claims (10)
1. a kind of catalyst of preparing cis-anhydride by n-butane oxidation, it is characterised in that catalyst body includes v element, P elements and oxygen
Element, it is aided with micro metal promoter；According to overall catalyst weight gauge, wherein containing：
V element is 26-35%,
P elements are 14-20%,
Oxygen element is 30-50%；
Metal promoter is 0.02-7%.
2. the catalyst of preparing cis-anhydride by n-butane oxidation as claimed in claim 1, it is characterised in that catalyst has rose
Structure；V element is selected from least one of the ammonium metavanadate after refining, vanadic anhydride or organic acid vanadium；Metal promoter is selected from
At least one of cobalt, bismuth, sodium, zirconium.
3. the preparation method of the catalyst of any one preparing cis-anhydride by n-butane oxidation in a kind of claim 1~2, its feature exist
In key step includes：Metal promoter is mixed with organic solvent first, vanadium source compound is then added, adds phosphorus source
Compound, after being heated to reflux 6-18h under continuous stirring, products therefrom filtration drying is obtained into vpo catalyst precursor powder,
Carry out being thermally treated resulting in catalyst at 300-500 DEG C.
4. the preparation method of the catalyst of preparing cis-anhydride by n-butane oxidation as claimed in claim 3, it is characterised in that vanadium source used
The particle size of compound is 1.5~3.5 μm.
5. the preparation method of the catalyst of preparing cis-anhydride by n-butane oxidation as claimed in claim 3, it is characterised in that phosphorus source
Compound is 0.8~1.3 with the P elements in vanadium source compound and the mol ratio of v element；Required organic solvent is with reduction
The alcohols solvent of ability.
6. the preparation method of the catalyst of preparing cis-anhydride by n-butane oxidation as claimed in claim 3, it is characterised in that the forerunner
Body powder uniformly obtains mixture A with mix lubricant；Said mixture A is placed in constant temperature constant humidity baking oven, handles 3~24h,
Thermostat temperature is 20~60 DEG C, and constant humidity humidity is relative humidity 40~95%；Powder compressing machine is used under 10~40MPa pressure
A compressing tablet process is carried out, obtains one-shot forming catalyst；By above-mentioned one-shot forming catalyst breakage, screening, grain graininess is taken
For the catalyst of 20~160 mesh, as pre-granulation particle；Above-mentioned pre-granulation particle is placed on rotary pelleting machine and carries out secondary pressure
Piece processing, obtain the hollow cylinder catalyst configuration thing that height is 4~6mm；Above-mentioned catalyst configuration thing is placed in 380~
In 500 DEG C of temperature heat treatment activation is carried out with activation phenomenon；The activation phenomenon is selected from lighter hydrocarbons, air, inert gas, water vapour
Or at least one of carbon dioxide；Described lubricant is selected from graphite, talcum powder, stearate.
7. the preparation method of the catalyst of preparing cis-anhydride by n-butane oxidation as claimed in claim 6, it is characterised in that mixture A
Constant temperature and humidity processing is carried out after middle addition pore creating material, the pore creating material is selected from stearic acid, soluble starch, sesbania powder, poly- second two
At least one of alcohol.
8. the preparation method of the catalyst of preparing cis-anhydride by n-butane oxidation as claimed in claim 7, it is characterised in that in pre-granulation
Pore creating material is added in particle again and carries out rotary tablet compression again afterwards, the pore creating material is selected from stearic acid, soluble starch, sesbania powder
At least one of.
9. the preparation method of the catalyst of preparing cis-anhydride by n-butane oxidation as claimed in claim 6, it is characterised in that it is described once
The pressure limit of compressing tablet process is 15~30MPa.
A kind of 10. method of preparing cis-anhydride by n-butane oxidation, using any one catalyst described in claim 1~9, its feature
It is, catalyst reacts with the butane raw material that molar concentration is 1-1.5% in fixed bed reactors, produces cis-butenedioic anhydride, and it reacts
Process conditions：Air speed is 1000~3000hr-1, reaction temperature be 300~500 DEG C, reaction pressure is normal pressure.
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| CN111097465A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of vanadium phosphorus oxide catalyst |
| CN114433151A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Vanadium phosphorus oxygen catalyst and preparation method and application thereof |
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| CN111097465A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of vanadium phosphorus oxide catalyst |
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| CN114433151B (en) * | 2020-10-31 | 2024-02-13 | 中国石油化工股份有限公司 | Vanadium phosphorus oxide catalyst and preparation method and application thereof |
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