CN106582745A - Method for refining vanadium source in vanadium phosphorous oxide catalyst - Google Patents
Method for refining vanadium source in vanadium phosphorous oxide catalyst Download PDFInfo
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- CN106582745A CN106582745A CN201510674651.3A CN201510674651A CN106582745A CN 106582745 A CN106582745 A CN 106582745A CN 201510674651 A CN201510674651 A CN 201510674651A CN 106582745 A CN106582745 A CN 106582745A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 51
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007670 refining Methods 0.000 title claims abstract description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title abstract 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 38
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 28
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 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
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 239000010955 niobium Substances 0.000 claims abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000007524 organic acids Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 14
- 239000001273 butane Substances 0.000 claims description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- 239000000600 sorbitol Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 241000220317 Rosa Species 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims 2
- 241000196324 Embryophyta Species 0.000 claims 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims 1
- 150000003138 primary alcohols Chemical class 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 abstract 3
- 229910021654 trace metal Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 22
- 235000013844 butane Nutrition 0.000 description 19
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 18
- 235000011007 phosphoric acid Nutrition 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 6
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 5
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 5
- 239000000811 xylitol Substances 0.000 description 5
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 5
- 229960002675 xylitol Drugs 0.000 description 5
- 235000010447 xylitol Nutrition 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
- 239000007787 solid Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011175 product filtration Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 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
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003742 xyloses Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
The present invention relates to a method for refining the vanadium source in a vanadium phosphorous oxide catalyst. In the prior art, the vanadium source for preparing the prepared vanadium phosphorous oxide catalyst has characteristics of large particle and low specific surface area so as to cause the poor performance of the generated catalyst. A purpose of the present invention is to mainly solve the problem in the prior art. The technical scheme of the present invention comprises that the main body comprises three elements such as vanadium, phosphorous and oxygen, a trace metal auxiliary agent is combined, the catalyst contains, by weight, 15-30% of vanadium element, 15-30% of phosphorus element, 15-35% o oxygen element, and 0.001-8% of the metal auxiliary agent, the vanadium element is at least one selected from refined ammonium metavanadate, vanadium pentoxide and organic acid vanadium, the metal auxiliary agent is at least one selected from lithium, niobium, bismuth and molybdenum, and a molar ratio of the phosphorus element to the vanadium element is 0.8-2.5. According to the present invention, the technical scheme for producing the vanadium source having the internal through pore structure by using the novel refining method can be used in the field of maleic anhydride preparation through n-butane oxidation.
Description
Technical field
The present invention relates to a kind of method for refining vanadium source in vanadium-phosphor oxide catalyst.
Background technology
Maleic anhydride, abbreviation cis-butenedioic anhydride, that is, maleic anhydride, are a kind of conventional important Organic Chemicals,
It is consumption figure is only second to phthalic anhydride and acetic anhydride in the world the third-largest anhydride kind.Cis-butenedioic anhydride is widely used in oil
The industries such as work, food chemistry, medicine, construction material, are mainly used in synthesizing unsaturated polyester resin, lubricating oil
Additive, food additive, 1,4- butanediols (BDO), gamma-butyrolacton (GBL), tetrahydrofuran (THF)
Etc. a series of important organic chemicals and fine chemicals.
The early stage production of cis-butenedioic anhydride is prepared by the selective oxidation of benzene, but the harm due to benzene to human body and environment
Property, and the impact 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 is inexpensive, pollute relatively light, carbon atom utilization rate height and maleic anhydride production low cost and other advantages,
Preparing cis-anhydride by n-butane oxidation technology is increasingly becoming 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,
Think that vanadium-phosphorus-oxygen (VPO) catalyst is still catalyst system maximally efficient so far.With regard to VPO
The preparation method of catalyst has substantial amounts of open source literature and patented technology, summarizes and is concentrated mainly on industrialization
Vpo catalyst be typically with aqueous solvent or organic solvent method presoma be obtained, gained presoma is by roasting
Burn activation and molding obtains final catalyst.As organic solvent method has relative to the catalyst that Aqueous phase is obtained
Larger specific surface area, therefore with certain advantage.This method is mainly with the single of isobutanol and benzyl alcohol
Or mixed system is solvent.Therefore, the preparation process of specific organic solvent method is that vanadium source is dissolved in organic solvent
In, reaction being stirred at reflux, and adds phosphorus source, continued backflow and obtain presoma, last heat treatment activation is urged
Agent.
But the research emphasis of these customary preparation methods all concentrate on the reaction effect for how improving vanadium source and phosphorus source
Really, and investigate the concentration of phosphorus source purity is higher, the more obvious vpo catalyst of shape characteristic to obtain.It is beautiful
State's patent US4374043 describe using mixing phosphorus source prepare catalyst, wherein mixing phosphorus source be orthophosphoric acid,
The mixture of pyrophosphoric acid and a small amount of triphosphoric acid.United States Patent (USP) US4365069 discloses and using 85% orthophosphoric acid is
The preparation method of phosphorus source.These methods all focus on to have investigated impact of the phosphorus source to catalyst, and ignore to vanadium source
Investigation, do not pay attention to impact of the subtractive process in vanadium source to vpo catalyst purity and pattern.
The content of the invention
One of the technical problem to be solved be in prior art due to vanadium source structure affect be catalyzed
The problem of dosage form looks and performance, discloses a kind of vanadium-phosphor oxide catalyst, the method in its new refined vanadium source, raw
Output particle diameter is 1-5 μm, specific surface area is 15-30m2/ g, the vanadium source with abundant pore passage structure, improves
The structure and morphology of catalyst, so as to improve the performance of catalyst.
The two of the technical problem to be solved are to provide a kind of corresponding with one of technical problem is solved
The preparation method of catalyst.
The three of the technical problem to be solved are to provide a kind of corresponding with one of technical problem is solved
The method for improving 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 vanadium-phosphor oxide catalyst,
Catalyst has rose structure；Its main body includes vanadium, phosphorus, oxygen element, is aided with micro metal promoter；
According to total catalyst weight, wherein being 15-30% containing v element, P elements are 15-30%, and oxygen element is
15-35%；Metal promoter is 0.001-8%.
In above-mentioned technical proposal, ammonium metavanadate of the vanadium source compound after refining, vanadic anhydride or organic acid
At least one of vanadium；Metal promoter is selected from lithium, niobium, bismuth, at least one of molybdenum.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of vanadium-phosphor oxide catalyst
Preparation method, key step includes：First vanadium source compound is mixed in organic solvent I, phosphorus is added
Source compound and metal promoter, after being heated to reflux 1-20h under continuous stirring, by products therefrom filtration drying,
Carry out being thermally treated resulting in catalyst at 200-500 DEG C.
In above-mentioned technical proposal, the particle size of vanadium source compound used is 1-5 μm.Phosphorus source compound with
P/V ratios in vanadium source compound are 0.8-1.5；Required organic solvent I is that the primary alconol class with reducing power is molten
Agent.
In above-mentioned technical proposal, for the preparation side of vanadium phosphorus oxygen (VPO) catalyst of preparing cis-anhydride by n-butane oxidation
Method, it is characterised in that vanadium source compound used before mixing with organic solvent I needed to be refined, which refines
Method is mainly included the following steps that：
(1) the vanadium source compound of technical grade is carried out into ball milling in ball mill；
(2) by the vanadium source compound after ball milling in organic solvent II agitator treating 1-10h, after sucking filtration will filter cake heat at
Reason 1-20h, obtains refined vanadium source.
In such scheme, described step (1), after vanadium source compound carries out ball milling, particle size is 1-15 μm,
Specific surface area is 5-15m2/g。
In above-mentioned technical proposal, described step (2), vanadium source compound in organic solvent II agitator treating and
After heat treatment, granule is 1-4 μm, and specific surface area is 25-30m2/g。
In above-mentioned technical proposal, the preparation method of described vanadium-phosphor oxide catalyst, it is characterised in that the thick vanadium of washing
The organic solvent II in source is the mixed solution of polyhydric alcohol and aromatic alcohol, wherein polyhydric alcohol selected from glycerol, xylitol or
At least one of Sorbitol, aromatic alcohol are selected from benzyl alcohol, and wherein hydroxyl and the mol ratio of v element are 1-10:1.
In above-mentioned technical proposal, preferred technical scheme is described hydroxyl and the mol ratio of v element is 2-8:1
In above-mentioned technical proposal, preferred technical scheme be organic solvent II be glycerol, xylitol, Sorbitol and
The mixture of benzyl alcohol, wherein the hydroxyl ratio of four kinds of alcohol is 1：1：1：1, and total hydroxyl and v element rub
You are than being (4～8)：1.
In above-mentioned technical proposal, it is characterised in that mixing speed of the vanadium source compound in organic solvent II be
100-600r/min, is 100-500 DEG C of roasting in air atmosphere to filter cake heat treatment process.
To solve the three of above-mentioned technical problem, the technical solution used in the present invention is as follows：It is a kind of to be used for normal butane oxygen
The method for changing cis-butenedioic anhydride processed, using any one vanadium-phosphor oxide catalyst described in claim 1～9, its feature exists
In, butane raw material of the vanadium-phosphor oxide catalyst with molar concentration for 1-1.5%mol is reacted in fixed bed reactors,
Production cis-butenedioic anhydride, its reaction process condition：Air speed is 1000～3000hr-1, reaction temperature be 300～500 DEG C,
Reaction pressure is normal pressure.
Using technical scheme, the vanadium source compound of technical grade is carried out after ball milling, in organic solvent
Agitator treating simultaneously carries out heat treatment, and the granular size that vanadium source compound is obtained is 1-5 μm, forms interior between granule
The pore passage structure of portion's insertion, specific surface area are 15-30m2/g.There is catalyst prepared by which rose to tie
Structure, substantially improves the catalytic performance of catalyst, and the yield of its oxidizing n-butane cis-butenedioic anhydride can reach 64%.
The present invention, but content not thereby limiting the invention are further illustrated with example below.
Description of the drawings
The SEM photograph in vanadium sources of the Fig. 1 by technical scheme after refined.
Fig. 2 is the SEM photograph in the vanadium source for being provided without process for purification process.
Specific embodiment
【Embodiment 1】
1 part of technical grade vanadic anhydride is carried out after ball milling, particle size is 1-15 μm, in 3 parts of glycerol and
500r/min stirrings 6h in the mixed solution of 1 part of benzyl alcohol, after sucking filtration in roaster roasting 6h at 400 DEG C,
Vanadic anhydride after being refined, its granule are 1-5 μm, and specific surface area is 26m2/ g, with abundant
Pore passage structure.After 30g vanadic anhydrides after above-mentioned exquisiteness are mixed with 280ml isobutanol, 32g is added
The phosphoric acid and 0.8g bismuth nitrate of 100wt%, is heated to reflux 16h under agitation, by products therefrom filtration drying,
Catalyst is thermally treated resulting at 400 DEG C.By gained catalyst and the butane raw material that molar concentration is 1.5%mol
Reaction, its reaction process condition：2000hr-1Check and rate in fixed bed reactors under air speed, 400 DEG C of normal pressures,
It is 85.1% to measure butanes conversion, and yield of maleic anhydride 62.4%, its appraisal result refer to table 1.
【Embodiment 2】
1 part of technical grade vanadic anhydride is carried out after ball milling, particle size is 1-15 μm, in 3 parts of xylitol
With 500r/min stirrings 6h, the roasting at 400 DEG C in roaster after sucking filtration in the mixed solution of 1 part of benzyl alcohol
6h, the vanadic anhydride after being refined, its granule are 1-5 μm, and specific surface area is 27m2/ g, with rich
Rich pore passage structure.After 30g vanadic anhydrides after above-mentioned exquisiteness are mixed with 280ml isobutanol, add
The phosphoric acid and 0.8g bismuth nitrate of 32g 100wt%, is heated to reflux 16h under agitation, by products therefrom filtration drying,
Catalyst is thermally treated resulting at 400 DEG C.By gained catalyst and the butane raw material that molar concentration is 1.5%mol
Reaction, its reaction process condition：2000hr-1Check and rate in fixed bed reactors under air speed, 400 DEG C of normal pressures,
It is 84.8% to measure butanes conversion, and yield of maleic anhydride 62.5%, its appraisal result refer to table 1.
【Embodiment 3】
1 part of technical grade vanadic anhydride is carried out after ball milling, particle size is 1-15 μm, in 3 parts of Sorbitol
With 500r/min stirrings 6h, the roasting at 400 DEG C in roaster after sucking filtration in the mixed solution of 1 part of benzyl alcohol
6h, the vanadic anhydride after being refined, its granule are 1-5 μm, and specific surface area is 26m2/ g, with rich
Rich pore passage structure.After 30g vanadic anhydrides after above-mentioned exquisiteness are mixed with 280ml isobutanol, add
The phosphoric acid and 0.8g bismuth nitrate of 32g 100wt%, is heated to reflux 16h under agitation, by products therefrom filtration drying,
Catalyst is thermally treated resulting at 400 DEG C.By gained catalyst and the butane raw material that molar concentration is 1.5%mol
Reaction, its reaction process condition：2000hr-1Check and rate in fixed bed reactors under air speed, 400 DEG C of normal pressures,
It is 84.6% to measure butanes conversion, and yield of maleic anhydride 62.1%, its appraisal result refer to table 1.
【Embodiment 4】
1 part of technical grade vanadic anhydride is carried out after ball milling, particle size be 1-15 μm, 1.5 parts of glycerol,
500r/min stirrings 6h in the mixed solution of 1.5 parts of xylitol and 1 part of benzyl alcohol, after sucking filtration in roaster
Roasting 6h at 400 DEG C, the vanadic anhydride after being refined, its granule are 1-4 μm, and specific surface area is 28
m2/ g, with abundant pore passage structure.30g vanadic anhydrides after above-mentioned exquisiteness are mixed with 280ml isobutanol
The phosphoric acid and 0.8g bismuth nitrate of 32g 100wt% after conjunction, are added, 16h is heated to reflux under agitation, by gained
Product filtration drying, is thermally treated resulting in catalyst at 400 DEG C.By gained catalyst and molar concentration it is
The butane raw material reaction of 1.5%mol, its reaction process condition：2000hr-1Solid under air speed, 400 DEG C of normal pressures
Check and rate in fixed bed reactor, it is 85.2% to measure butanes conversion, and yield of maleic anhydride 63.5%, its appraisal result are detailed
It is shown in Table 1.
【Embodiment 5】
1 part of technical grade vanadic anhydride is carried out after ball milling, particle size be 1-15 μm, 1.5 parts of glycerol,
500r/min stirrings 6h in the mixed solution of 1.5 parts of Sorbitol and 1 part of benzyl alcohol, after sucking filtration in roaster
Roasting 6h at 400 DEG C, the vanadic anhydride after being refined, its granule are 1-4 μm, and specific surface area is 29
m2/ g, with abundant pore passage structure.30g vanadic anhydrides after above-mentioned exquisiteness are mixed with 280ml isobutanol
The phosphoric acid and 0.8g bismuth nitrate of 32g 100wt% after conjunction, are added, 16h is heated to reflux under agitation, by gained
Product filtration drying, is thermally treated resulting in catalyst at 400 DEG C.By gained catalyst and molar concentration it is
The butane raw material reaction of 1.5%mol, its reaction process condition：2000hr-1Solid under air speed, 400 DEG C of normal pressures
Check and rate in fixed bed reactor, it is 85.1% to measure butanes conversion, and yield of maleic anhydride 63.3%, its appraisal result are detailed
It is shown in Table 1.
【Embodiment 6】
1 part of technical grade vanadic anhydride is carried out after ball milling, particle size is 1-15 μm, in 1.5 parts of xyloses
500r/min stirrings 6h in the mixed solution of alcohol, 1.5 parts of Sorbitol and 1 part of benzyl alcohol, in roaster after sucking filtration
In roasting 6h at 400 DEG C, the vanadic anhydride after being refined, its granule are 1-4 μm, and specific surface area is
29m2/ g, with abundant pore passage structure.By 30g vanadic anhydrides and 280ml isobutyls after above-mentioned exquisiteness
The phosphoric acid and 0.8g bismuth nitrate of 32g 100wt% after alcohol mixing, are added, 16h is heated to reflux under agitation, will
Products therefrom filtration drying, is thermally treated resulting in catalyst at 400 DEG C.By gained catalyst and molar concentration it is
The butane raw material reaction of 1.5%mol, its reaction process condition：2000hr-1Solid under air speed, 400 DEG C of normal pressures
Check and rate in fixed bed reactor, it is 85.4% to measure butanes conversion, and yield of maleic anhydride 63.4%, its appraisal result are detailed
It is shown in Table 1.
【Embodiment 7】
1 part of technical grade vanadic anhydride is carried out after ball milling, particle size be 1-15 μm, 1 part of glycerol,
In the mixed solution of 1 part of xylitol, 1 part of Sorbitol and 1 part of benzyl alcohol 500r/min stirring 6h, after sucking filtration
Roasting 6h at 400 DEG C in roaster, the vanadic anhydride after being refined, its granule are 2-4 μm, specific surface
Product is 30m2/ g, with abundant pore passage structure.By 30g vanadic anhydrides and 280ml after above-mentioned exquisiteness
The phosphoric acid and 0.8g bismuth nitrate of 32g 100wt% after isobutanol mixing, are added, 16h is heated to reflux under agitation,
By products therefrom filtration drying, catalyst is thermally treated resulting at 400 DEG C.By gained catalyst and molar concentration
For the butane raw material reaction of 1.5%mol, its reaction process condition：2000hr-1Under air speed, 400 DEG C of normal pressures
Check and rate in fixed bed reactors, it is 85.4% to measure butanes conversion, yield of maleic anhydride 63.4%, its appraisal result
Refer to table 1.
【Comparative example 1】
1 part of technical grade vanadic anhydride is carried out after ball milling, particle size is 1-15 μm, specific surface area is
14m2/g.After 30g vanadic anhydrides after above-mentioned exquisiteness are mixed with 280ml isobutanol, 32g is added
The phosphoric acid and 0.8g bismuth nitrate of 100wt%, is heated to reflux 16h under agitation, by products therefrom filtration drying,
Catalyst is thermally treated resulting at 400 DEG C.By gained catalyst and the butane raw material that molar concentration is 1.5%mol
Reaction, its reaction process condition：2000hr-1Check and rate in fixed bed reactors under air speed, 400 DEG C of normal pressures,
It is 83.1% to measure butanes conversion, and yield of maleic anhydride 59.7%, its appraisal result refer to table 1.
【Comparative example 2】
After 30g technical grades vanadic anhydride is mixed with 280ml isobutanol, the phosphoric acid of 32g 100wt% is added
With 0.8g bismuth nitrate, 16h is heated to reflux under agitation, by products therefrom filtration drying, at heat at 400 DEG C
Reason obtains catalyst.By gained catalyst and the butane raw material reaction that molar concentration is 1.5%mol, its reaction
Process conditions：2000hr-1Check and rate in fixed bed reactors under air speed, 400 DEG C of normal pressures, measure conversion of butane
Rate is 83.6%, and yield of maleic anhydride 57.1%, its appraisal result refer to table 1.
Table 1
Claims (10)
1. a kind of vanadium-phosphor oxide catalyst, it is characterised in that catalyst has rose structure；Its main body bag
V element, P elements and oxygen element are included, is aided with micro metal promoter；According to overall catalyst weight gauge, wherein
Contain：V element is 15-30%, and P elements are 15-30%, and oxygen element is 15-35%；Metal promoter is
0.001-8%；
Wherein, at least the one of ammonium metavanadate of the v element after refining, vanadic anhydride or organic acid vanadium
Kind；At least one of the metal promoter in lithium, niobium, bismuth, molybdenum；
Wherein described P elements are 0.8-2.5 with the mol ratio of v element.
2. in a kind of claim 1 vanadium-phosphor oxide catalyst preparation method, it is characterised in that key step bag
Include：First vanadium source compound is mixed in organic solvent I, P source compound and metal promoter is added,
After 1-20h is heated to reflux under persistently stirring, by products therefrom filtration drying, hot place is carried out at 200-500 DEG C
Reason obtains catalyst.
3. the preparation method of vanadium-phosphor oxide catalyst as claimed in claim 2, it is characterised in that vanadium source used
The particle size of compound is 1-5 μm.
4. the preparation method of vanadium-phosphor oxide catalyst as claimed in claim 2, it is characterised in that required phosphorus source
Compound is 0.8-1.5 with the P/V mol ratios in vanadium source compound；The organic solvent I is with also proper energy
The primary alcohols solvent of power.
5. the preparation method of vanadium-phosphor oxide catalyst as claimed in claim 2, it is characterised in that vanadium source used
Compound before mixing with organic solvent I needed to be refined, and its process for purification is mainly included the following steps that：
(1) the vanadium source compound of technical grade is carried out into ball milling in ball mill；
(2) by the vanadium source compound after ball milling in organic solvent II agitator treating 1-10h, after sucking filtration will filter cake heat at
Reason 1-20h, obtains refined vanadium source compound.
6. the preparation method of vanadium-phosphor oxide catalyst as claimed in claim 5, it is characterised in that described essence
The pore passage structure of internal run-through is formed between vanadium source compound granule processed, specific surface area is 15-30m2/g。
7. the preparation method of vanadium-phosphor oxide catalyst as claimed in claim 5, it is characterised in that washing vanadium source
The organic solvent II of compound is the mixed solution of polyhydric alcohol and aromatic alcohol, and wherein polyhydric alcohol is selected from glycerol, xylose
At least one in alcohol or Sorbitol, aromatic alcohol are selected from benzyl alcohol；Wherein hydroxyl with the mol ratio of v element is
(1-10):1。
8. the preparation method of vanadium-phosphor oxide catalyst as claimed in claim 7, it is characterised in that hydroxyl and vanadium
The mol ratio of element is (2-8):1.
9. the preparation method of vanadium-phosphor oxide catalyst as claimed in claim 5, it is characterised in that vanadium source chemical combination
Mixing speed of the thing in organic solvent II is 100-600r/min, is in air atmosphere to filter cake heat treatment process
Lower 100-500 DEG C of roasting.
10. a kind of method for preparing cis-anhydride by n-butane oxidation, using any one described in claim 1～9
Plant catalyst, it is characterised in that catalyst is with the butane raw material that molar concentration is 1-1.5% in fixed bed reaction
React in device, produce cis-butenedioic anhydride, its reaction process condition：Air speed is 1000～3000hr-1, reaction temperature be
300～500 DEG C, reaction pressure is normal pressure.
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| CN109550515A (en) * | 2017-09-30 | 2019-04-02 | 中国科学院过程工程研究所 | A kind of preparation method and application of vanadium-phosphor oxide catalyst |
| CN116020504A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | A kind of n-butane oxidation catalyst and its preparation method and application |
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