CN106000434A - Maleic anhydride catalyst and preparation method thereof - Google Patents
Maleic anhydride catalyst and preparation method thereof Download PDFInfo
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- CN106000434A CN106000434A CN201610345873.5A CN201610345873A CN106000434A CN 106000434 A CN106000434 A CN 106000434A CN 201610345873 A CN201610345873 A CN 201610345873A CN 106000434 A CN106000434 A CN 106000434A
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- maleic anhydride
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- anhydride catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000013078 crystal Substances 0.000 claims abstract description 44
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 40
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000540 VOPO4 Inorganic materials 0.000 claims abstract description 34
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000004913 activation Effects 0.000 claims abstract description 23
- 238000010992 reflux Methods 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 230000015572 biosynthetic process Effects 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 229960004217 benzyl alcohol Drugs 0.000 abstract 1
- 229940035429 isobutyl alcohol Drugs 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 11
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000001273 butane Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- -1 divides two classes Chemical compound 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical compound [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 description 1
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 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
- B01J35/60—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a maleic anhydride catalyst and a preparation method thereof. The maleic anhydride catalyst consists of (VO) 2P2O7 crystals and VOPO4 crystal forms, wherein the VOPO4 crystal forms account for 1 percent to 5 percent of the mass percentage composition of the maleic anhydride catalyst. The preparation method comprises the following steps that vanadium pentoxide is put into mixed liquid formed by phenylcarbinol, isobutyl alcohol and an auxiliary agent; heating refluxing is performed; then, phosphoric acid is added for continuous refluxing; next, solid-liquid separation, drying, pressing forming and high-temperature roasting activation are performed; then, the maleic anhydride catalyst is obtained, wherein the obtained maleic anhydride catalyst consists of (VO)2P2O7 crystals and VOPO4 crystal forms, and the mass percentage composition of the VOPO4 crystal forms in the total quantity of the maleic anhydride catalyst meets the following formula shown as the accompanying drawing. The maleic anhydride catalyst provided by the invention has the advantages of high intensity, high specific surface area, high conversion rate, high selectivity and high yield.
Description
Technical field
The invention belongs to catalyst technical field, specifically, relate to a kind of maleic anhydride catalyst and preparation method thereof.
Background technology
Maleic anhydride, is called for short cis-butenedioic anhydride, that is maleic anhydride, is a kind of conventional important Organic Chemicals, the world
The anhydride kind that upper consumption is the third-largest.Cis-butenedioic anhydride is currently used primarily in production unsaturated polyester resin, alkyd resin, 1,4-butanediol
(BDO), the chemicals such as gamma-butyrolacton (GBL), oxolane (THF).Additionally, also have extensively at all kinds of Field of Fine Chemicals
Application.
The production of cis-butenedioic anhydride mainly divides two classes, production method the earliest use benzene as raw materials for production, but due to raw material itself
With the hazardness to environment, and the impact of economic factor, the ratio shared in maleic anhydride production of the production technology of benzene method is day by day
Reduce；The main flow production method employing normal butane of cis-butenedioic anhydride is as raw materials for production at present, including fixed bed, fluid bed, moving bed etc.,
These techniques are respectively arranged with feature, the most all have the commercial Application of reality, but identical, the work of these preparing cis-anhydride by n-butane oxidation
Skill, all uses same class catalyst, i.e. vanadium phosphorus oxygen (VPO) catalyst.
Cis-butenedioic anhydride is extensively applied for market as a kind of basic technical synthetic materials, and the key element of its synthesis is suitable
The performance of acid anhydride catalyst, directly affects the yield of maleic anhydride production, cost, quality, energy consumption and environmental protection degree.
The catalyst of preparing cis-anhydride by n-butane oxidation the most often tried multiple catalysts in early days, but confirmed through years of researches
Vpo catalyst is still the most maximally efficient catalyst system.Conventional vpo catalyst uses aqueous solvent or organic solvent
Legal system obtains presoma, and gained presoma obtains final catalyst by calcination activation and molding.At present, the VPO of industrial applications
Catalyst all uses unsupported catalyst.Owing to vpo catalyst existence itself is as less in specific surface area, intensity is relatively low, heat transfer effect
The shortcoming such as the poorest.
At present, the catalyst needed for China Maleic Anhydrite production, mainly it is derived from foreign technology or directly import, its performance indications
Far above domestic about colleges and universities, the sample of scientific research institutions' research and development, this is also that domestic catalyst delays to substitute the main of import
Reason.
Propose the preparation method of many catalyst precursors both at home and abroad, as CN1059297A discloses a kind of for fluidizing
Bed n butane oxidation prepares the preparation method of V-P-O series catalysts of cis-butenedioic anhydride, the method be with technical grade vanadic anhydride and
85% phosphoric acid is raw material, with isobutanol as reducing agent, carries out reduction reaction under conditions of heating, then through heat filter, modification,
Add metal promoters, size mixing, be spray-dried and obtain microspherical catalyst.At the method metal promoters to be added and modification
Reason, preparation flow is long, and the activity and selectivity of catalyst is the highest.
CN1133755A discloses a kind of preparation method preparing maleic anhydride catalyst for n-butane in fluidized bed catalysis oxidation,
The method include catalyst precursor preparation and the post processing course of processing.The preparation of presoma is with vanadic anhydride and phosphoric acid
For raw material, with hydrazine hydrate as reducing agent, with the mixed liquor of benzyl alcohol and isobutanol as solvent, course of reaction adds iron ion
Or zirconium ion, the precursor obtained and Ludox and gellant make supported catalyst slurry, then drying dehydration, certain
Atmosphere and at a temperature of activate, last molding screening obtain finished catalyst.The method has long flow path equally and activating process is multiple
Miscellaneous shortcoming.
CN1282631A discloses the preparation method of a kind of vanadium-phosphorus-oxide catalysts, and the method is with dense by vanadic anhydride
After hydrochloric acid is heated to reflux, adds phosphoric acid and continue backflow, after cooling, add zirconium nitrate, ammonium molybdate and zinc acetate.This catalyst
Complicated component, and it is the highest to be catalyzed activity and selectivity.
CN1303741A describes the preparation method of the compound vanadium-phosphorus-oxide catalysts of a kind of preparing cis-anhydride by n-butane oxidation, should
Method be by vpo catalyst add storage oxysome ceria base composite oxidate increase catalyst system can oxygen consuming amount,
Catalyst component prepared by the method is complicated, adds expensive rare earth oxide.
US5108974 discloses the preparation method of a kind of vanadium-phosphorus-oxide catalyst precursor, and the method is by just
In the presence of alkyl silicate and phosphate mixture, in alcoholic solvent, vanadic anhydride is added and be heat reduced to vanadium tetraoxide (V2O4),
In the presence of tetraalkyl orthosilicate, product generates precipitation with remaining phosphoric acid.
It is particularly effective that US4294722A discloses a kind of oxidation to normal butane containing vanadium phosphorus mixed oxide catalyst
The preparation method of oxidation catalyst, the method is to be dissolved in isobutanol by vanadic anhydride, is heated at reflux about 16 hours；By phosphoric acid
Being dissolved in isobutanol and add in above-mentioned filtrate, the mixture obtained is heated to reflux 8 hours；Cooling is collected precipitate and is urged
Agent precursor.Selectivity and the yield of cis-butenedioic anhydride are the most relatively low.
As it has been described above, the catalyst of preparation method preparation production cis-butenedioic anhydride there is also cis-butenedioic anhydride productivity and selectivity in prior art
The shortcomings such as the highest, preparation process length.
In view of this special proposition present invention.
Summary of the invention
For overcoming the deficiencies in the prior art, the first object of the present invention is that a kind of maleic anhydride catalyst of offer, this cis-butenedioic anhydride
Catalyst has high intensity, high-specific surface area, and has the advantage that conversion ratio is high, selectivity is high, yield is high.
The second object of the present invention is to provide the preparation method of above-mentioned maleic anhydride catalyst, the method to have yield height, choosing
The advantages such as selecting property is high and preparation process is simple.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of maleic anhydride catalyst, wherein, described maleic anhydride catalyst is by (VO)2P2O7Crystal and VOPO4Crystal formation forms, its
Middle VOPO4It is 1%～5% that crystal formation accounts for the weight/mass percentage composition of described maleic anhydride catalyst.
The present inventor studies discovery, the quality of maleic anhydride catalyst performance through for a long time and in depth, depends primarily on catalysis
The synthesis quality of agent presoma and level, secondly, the high temperature gas phase condition needed for presoma is carried out calcination activation the most quite closes
Key.And the building-up process of presoma, seem simple, actually complicated, relate to quantity relative ratio relationship sensitive between multiple reactant.Adopt
The presoma synthesized by different additional proportions, different control conditions, its crystal formation kind, be distributed with constitute widely different,
Cause performance difference the biggest.Owing to V has multiple valence state, the crystalline phase composition complexity of catalyst, the proportioning of multiple valence state V and association
It is mainly (VOPO with effect4) (i.e. V5+) and ((VO)2P2O7) (i.e. V4+) synergism constitute the active center of catalytic reaction
System.On this basis, the present inventor finds, when described maleic anhydride catalyst is by (VO) through substantial amounts of test2P2O7Crystal and
VOPO4Crystal formation forms, and works as VOPO4Crystal formation accounts for the weight/mass percentage composition of described maleic anhydride catalyst when being 1%～5%, obtained
Maleic anhydride catalyst there is high intensity, high-specific surface area, its conversion ratio is high, selectivity is high, yield is high.
The preparation method of maleic anhydride catalyst provided by the present invention include being placed in vanadic anhydride benzyl alcohol, isobutanol and
Auxiliary agent composition mixed liquor in be heated to reflux, add phosphoric acid continue backflow, then through solid-liquid separation, dry, compressing and
Obtaining maleic anhydride catalyst after high-temperature roasting activation, wherein, described maleic anhydride catalyst is by (VO)2P2O7Crystal and VOPO4Crystal formation group
Become, described VOPO4Crystal formation weight/mass percentage composition in maleic anhydride catalyst total amount meets equation below:
In formula:
J represents VOPO4Crystal formation percentage composition in maleic anhydride catalyst total amount；
V represents vanadic anhydride quality；
P represents phosphoric acid quality；
B represents benzyl alcohol quality；
I represents isobutanol quality；
M represents auxiliary agent quality；
R, r are two constants, wherein 0.1≤R≤10 respectively, 0.1≤r≤10.
Owing to V has multiple valence state, the crystalline phase composition complexity of catalyst, individually (VO)2P2O7It it not normal butane selectivity
The active phase of preparing cis-butenedioic anhydride by oxidation, the proportioning of multiple valence state V and cooperative effect are mainly (VOPO4) (i.e. V5+) and ((VO)2P2O7)
(i.e. V4+) synergism constitute the active center system of catalytic reaction, suitable V4+With V5+Equilibrium state particularly significant.And
The building-up process of presoma relates between multiple reactant sensitive quantity relative ratio relationship, uses different additional proportion, different
The presoma of control condition synthesis, its crystal formation kind, V4+With V5+Distribution proportion with constitute widely different, cause performance difference
The biggest.Select the amount ratio between suitable each reactant, find out itself and V4+、V5+Between proportion relation to whether obtaining
The maleic anhydride catalyst with high-quality performance is particularly important.The present inventor studies discovery through for a long time and in depth, works as gained
Maleic anhydride catalyst in VOPO4When crystal formation weight/mass percentage composition in maleic anhydride catalyst total amount meets above-mentioned formula, gained
Maleic anhydride catalyst has the advantage that high intensity, high-specific surface area and conversion ratio are high, selectivity is high, yield is high.
In above-mentioned preparation method, wherein, on the basis of vanadic anhydride quality, each reactant quality proportionate relationship is V:P:
B:I:M=1:(1.077～1.267): (0.01～10): (0.813～10): (0.002～0.2).
Preferably, in above-mentioned preparation method, described high-temperature roasting activation is mixed be made up of water vapour, air and nitrogen
Close in gas and carry out.
Further, in described mixed gas, the volume ratio of water vapour, air and nitrogen is 1:(0.1～1): (0.1～
1)。
Further, when carrying out high-temperature roasting activation, air speed is 1200～2400h-1；Temperature is 360～450 DEG C.
In the present invention, described in time of being heated to reflux be 1～24 hour, the described time continuing backflow is 1～24 hour,
When refluxing total a length of 12～30 hours.
For above-mentioned maleic anhydride catalyst, the present invention also provides for another kind of preparation method, and the method includes vanadic anhydride
It is placed in the mixed liquor of benzyl alcohol, isobutanol and auxiliary agent composition and is heated to reflux, add phosphoric acid and continue backflow, then divide through solid-liquid
Maleic anhydride catalyst is obtained, it is characterised in that with vanadic anhydride quality be after, dry, compressing and high-temperature roasting activation
Benchmark, the mass ratio relation of each reactant is vanadic anhydride: phosphoric acid: benzyl alcohol: isobutanol: auxiliary agent=1:(1.077～
1.267): (0.01～10): (0.813～10): (0.002～0.2).
The present inventor studies discovery through for a long time and in depth, when the proportioning of each reactant meets above-mentioned mass ratio relation
Time, the maleic anhydride catalyst of gained has the advantage that high intensity, high-specific surface area and conversion ratio are high, selectivity is high, yield is high.
In above-mentioned preparation method, described high-temperature roasting activation is at the gaseous mixture being made up of water vapour, air and nitrogen
Carrying out in body, in wherein said mixed gas, the volume ratio of water vapour, air and nitrogen is 1:(0.1～1): (0.1～1)；
Preferably, when carrying out high-temperature roasting activation, air speed is 1200～2400h-1；Temperature is 360～450 DEG C.
The described time being heated to reflux is 1～24 hour, and the described time continuing backflow is 1～24 hour, when refluxing total
A length of 12～30 hours.
Described auxiliary agent is the compound containing molybdenio, compound containing cerio or containing in the compound of zirconio
One or more.
In the present invention, known to the described compressing man skilled in the art of passing through, knowledge and this technology are led
Forming method general in territory, adds binding agent molding conventional in the art, make lamellar, column, pellet, ring-type,
Any suitable shapes such as spherical, graininess, abnormity granule.
As a kind of preferred version, the compressing Characteristics of Abnormal Shape Catalyst Particles for a kind of butane oxidation cis-butenedioic anhydride of the present invention,
This Characteristics of Abnormal Shape Catalyst Particles is described in detail in ZL201520722058.7.
Compared with prior art, present invention have the advantage that
(1) maleic anhydride catalyst provided by the present invention has high intensity, high-specific surface area, and has conversion ratio height, selects
Property high, advantage that yield is high；
(2) preparation method of maleic anhydride catalyst provided by the present invention has yield height, selectivity is high and preparation process is simple
The advantages such as list.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below in conjunction with the embodiment of the present invention,
Being clearly and completely described the technical scheme in embodiment, following example are used for illustrating the present invention, but are not limited to
The scope of the present invention.
Embodiment 1
1) vanadic anhydride 1g≤V≤100g is placed in benzyl alcohol 1g≤B≤100g, isobutanol 1g≤I≤100g and helps
The mixed liquor of agent 0.02g≤M≤20g composition is heated to reflux 1 hour；Wherein, described auxiliary agent is 0.02≤M≤20g seven molybdenum
Acid ammonium；
2) it is subsequently adding phosphatase 11 g≤P≤126.7g, continues backflow 11 hours；
3) after completion of the reaction, carry out solid-liquid separation, be dried, obtain maleic anhydride catalyst presoma；
4) by the repressed molding of maleic anhydride catalyst presoma of gained, high temperature 400 DEG C, gas phase ratio (water vapour, air and
The volume ratio of nitrogen is 1:0.6:0.4), air speed 2000m3/h；Calcination activation obtains maleic anhydride catalyst；
The maleic anhydride catalyst of gained is by (VO)2P2O7Crystal and VOPO4Crystal formation forms, described VOPO4Crystal formation is urged at cis-butenedioic anhydride
Weight/mass percentage composition in agent total amount is 1%, and meets equation below:
In formula:
J represents VOPO4Crystal formation percentage composition in maleic anhydride catalyst total amount, J is 1%；
V represents vanadic anhydride quality；
P represents phosphoric acid quality；
B represents benzyl alcohol quality；
I represents isobutanol quality；
M represents auxiliary agent quality；
R, r are two constants, wherein 0.1≤R≤10 respectively, 0.1≤r≤10.
Embodiment 2
Concrete steps are with embodiment 1, except that step 1) in heating reflux reaction be 11 hours, step 2) in
Reflux time is 1 hour；In the maleic anhydride catalyst of gained, VOPO4Crystal formation percent mass in maleic anhydride catalyst total amount
Content is 5%.
Embodiment 3
Concrete steps are with embodiment 1, except that step 1) in be heated to reflux 10 hours, step 2) in continue backflow
20 hours；In the maleic anhydride catalyst of gained, VOPO4Crystal formation weight/mass percentage composition in maleic anhydride catalyst total amount is 3%.
Embodiment 4
Concrete steps are with embodiment 1, except that step 1) in be heated to reflux 15 hours, step 2) in continue backflow
5 hours；In the maleic anhydride catalyst of gained, VOPO4Crystal formation weight/mass percentage composition in maleic anhydride catalyst total amount is 4%.
Embodiment 5
In preparation method, on the basis of vanadic anhydride quality, controlling each reactant quality proportionate relationship is V:P:B:I:M
=1:1.077:0.01:0.813:0.002, other is same as in Example 1；In the maleic anhydride catalyst of gained, VOPO4Crystal formation exists
Weight/mass percentage composition in maleic anhydride catalyst total amount is 3%.
Embodiment 6
In preparation method, step 4) described in high-temperature roasting activation be mixed be made up of water vapour, air and nitrogen
Closing in gas and carry out, wherein in mixed gas, the volume ratio of water vapour, air and nitrogen is 1:0.1:0.1, other and embodiment 1
Identical；In the maleic anhydride catalyst of gained, VOPO4Crystal formation weight/mass percentage composition in maleic anhydride catalyst total amount is 3.5%.
Embodiment 7
In preparation method, step 4) described in high-temperature roasting activation be mixed be made up of water vapour, air and nitrogen
Closing in gas and carry out, wherein in mixed gas, the volume ratio of water vapour, air and nitrogen is 1:1:1, and air speed is 1200h-1, temperature
Being 360 DEG C, other is same as in Example 1；In the maleic anhydride catalyst of gained, VOPO4Crystal formation matter in maleic anhydride catalyst total amount
Amount percentage composition is 2.5%.
Embodiment 8
In preparation method, on the basis of vanadic anhydride quality, controlling each reactant quality proportionate relationship is V:P:B:I:M
=1:1.267:10:10:0.2, step 4) described in high-temperature roasting activation be mixed be made up of water vapour, air and nitrogen
Closing in gas and carry out, wherein in mixed gas, the volume ratio of water vapour, air and nitrogen is 1:0.5:0.5, and air speed is 2400h-1,
Temperature is 450 DEG C, and other is same as in Example 1；In the maleic anhydride catalyst of gained, VOPO4Crystal formation is in maleic anhydride catalyst total amount
Weight/mass percentage composition be 4.8%.
Embodiment 9
In preparation method, on the basis of vanadic anhydride quality, controlling each reactant quality proportionate relationship is V:P:B:I:M
=1:1.155:5:5:0.1, step 4) described in high-temperature roasting activation be in the mixing being made up of water vapour, air and nitrogen
Carrying out in gas, wherein in mixed gas, the volume ratio of water vapour, air and nitrogen is 1:0.4:0.4, and air speed is 2000h-1, temperature
Degree is 400 DEG C, and other is same as in Example 1；In the maleic anhydride catalyst of gained, VOPO4Crystal formation is in maleic anhydride catalyst total amount
Weight/mass percentage composition is 3.2%.
Embodiment 10
In preparation method, on the basis of vanadic anhydride quality, controlling each reactant quality proportionate relationship is V:P:B:I:M
=1:1.115:0.855:2.555:0.115, step 4) described in high-temperature roasting activation be by water vapour, air and nitrogen
Carrying out in the mixed gas of composition, wherein in mixed gas, the volume ratio of water vapour, air and nitrogen is 1:0.6:0.6, air speed
For 1800h-1, temperature is 380 DEG C, and other is same as in Example 1；In the maleic anhydride catalyst of gained, VOPO4Crystal formation is catalyzed at cis-butenedioic anhydride
Weight/mass percentage composition in agent total amount is 2.8%.
Embodiment 11
1) vanadic anhydride is placed in the mixed liquor of benzyl alcohol, isobutanol and auxiliary agent composition and is heated to reflux 1 hour；Its
In, described auxiliary agent is zirconium nitrate；
2) it is subsequently adding phosphoric acid, continues backflow 24 hours；
3) after completion of the reaction, carry out solid-liquid separation, be dried, obtain maleic anhydride catalyst presoma；
4) by the repressed molding of maleic anhydride catalyst presoma of gained, high temperature 400 DEG C, gas phase ratio (water vapour, air and
The volume ratio of nitrogen is 1:0.2:0.5), air speed 2000h-1；Calcination activation obtains maleic anhydride catalyst；The maleic anhydride catalyst of gained
In, VOPO4Crystal formation weight/mass percentage composition in maleic anhydride catalyst total amount is 3%.
Wherein, on the basis of vanadic anhydride quality, the mass ratio relation of each reactant is vanadic anhydride: phosphoric acid:
Benzyl alcohol: isobutanol: auxiliary agent=1:1.200:6:8:0.005.
Embodiment 12
1) vanadic anhydride is placed in the mixed liquor of benzyl alcohol, isobutanol and auxiliary agent composition and is heated to reflux 24 hours；Its
In, described auxiliary agent is cerium oxide；
2) it is subsequently adding phosphoric acid, continues back flow reaction 1 hour；
3) after completion of the reaction, carry out solid-liquid separation, be dried, obtain maleic anhydride catalyst presoma；
4) by the repressed molding of maleic anhydride catalyst presoma of gained, high temperature 360 DEG C, gas phase ratio (water vapour, air and
The volume ratio of nitrogen is 1:0.1:0.1), air speed 1200h-1；Calcination activation obtains maleic anhydride catalyst；
Wherein, on the basis of vanadic anhydride quality, the mass ratio relation of each reactant is vanadic anhydride: phosphoric acid:
Benzyl alcohol: isobutanol: auxiliary agent=1:1.077:0.01:0.813:0.002.In the maleic anhydride catalyst of gained, VOPO4Crystal formation is suitable
Weight/mass percentage composition in acid anhydride catalyst total amount is 1%.
Embodiment 13
1) vanadic anhydride is placed in the mixed liquor of benzyl alcohol, isobutanol and auxiliary agent composition and is heated to reflux 15 hours；Its
In, described auxiliary agent is ammonium heptamolybdate；
2) it is subsequently adding phosphoric acid, continues backflow 9 hours；
3) after completion of the reaction, carry out solid-liquid separation, be dried, obtain maleic anhydride catalyst presoma；
4) by the repressed molding of maleic anhydride catalyst presoma of gained, high temperature 450 DEG C, gas phase ratio (water vapour, air and
The volume ratio of nitrogen is 1:1:1), air speed 2400h-1；Calcination activation obtains maleic anhydride catalyst；
Wherein, on the basis of vanadic anhydride quality, the mass ratio relation of each reactant is vanadic anhydride: phosphoric acid:
Benzyl alcohol: isobutanol: auxiliary agent=1:1.267:10:10:0.2.In the maleic anhydride catalyst of gained, VOPO4Crystal formation is catalyzed at cis-butenedioic anhydride
Weight/mass percentage composition in agent total amount is 5%.
Test example 1
This test example uses fixed bed reactors, in air speed 1800h-1, butane concentration 1.8%, temperature 380～400 DEG C
Under the conditions of, investigate VOPO in maleic anhydride catalyst4Impact on catalyst performance during weight/mass percentage composition difference shared by crystal formation.
The results are shown in Table shown in 1:
Table 1
From above-mentioned result of the test it can be seen that work as VOPO4It is 1% that crystal formation accounts for the weight/mass percentage composition of described maleic anhydride catalyst
～when 5%, obtained maleic anhydride catalyst has high intensity, high-specific surface area, its conversion ratio is high, selectivity is high, yield is high.
Test example 2, evaluating catalyst result
Use fixed bed reactors, in air speed 1800h-1, butane concentration 1.8%, under conditions of temperature 380～400 DEG C, right
Catalyst obtained by the present invention is checked and rated, and result is as shown in table 2:
Table 2
The above is only presently preferred embodiments of the present invention, and the present invention not makees any pro forma restriction, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any technology people being familiar with the present invention
Member is in the range of without departing from technical solution of the present invention, when the technology contents of available above-mentioned prompting makes a little change or modification
For the Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit of the foundation present invention
Any simple modification, equivalent variations and the modification being made above example, all still falls within the range of the present invention program.
Claims (10)
1. a maleic anhydride catalyst, it is characterised in that described maleic anhydride catalyst is by (VO)2P2O7Crystal and VOPO4Crystal formation forms,
Wherein VOPO4It is 1%～5% that crystal formation accounts for the weight/mass percentage composition of described maleic anhydride catalyst.
2. a preparation method for the maleic anhydride catalyst described in claim 1, including vanadic anhydride is placed in benzyl alcohol, isobutyl
The mixed liquor of alcohol and auxiliary agent composition is heated to reflux, adds phosphoric acid and continue backflow, then through solid-liquid separation, be dried, be pressed into
Maleic anhydride catalyst is obtained, it is characterised in that described maleic anhydride catalyst is by (VO) after type and high-temperature roasting activation2P2O7Crystal and
VOPO4Crystal formation forms, described VOPO4Crystal formation weight/mass percentage composition in maleic anhydride catalyst total amount meets equation below:
In formula:
J represents VOPO4Crystal formation percentage composition in maleic anhydride catalyst total amount；
V represents vanadic anhydride quality；
P represents phosphoric acid quality；
B represents benzyl alcohol quality；
I represents isobutanol quality；
M represents auxiliary agent quality；
R, r are respectively two constants, wherein 0.1≤R≤10,0.1≤r≤10.
Preparation method the most according to claim 2, it is characterised in that on the basis of vanadic anhydride quality, each reactant
Mass ratio relation be V:P:B:I:M=1:(1.077～1.267): (0.01～10): (0.813～10): (0.002～
0.2)。
Preparation method the most according to claim 3, it is characterised in that described high-temperature roasting activation be by water vapour,
The mixed gas of air and nitrogen composition is carried out.
Preparation method the most according to claim 4, it is characterised in that water vapour, air and nitrogen in described mixed gas
The volume ratio of gas is 1:(0.1～1): (0.1～1).
Preparation method the most according to claim 5, it is characterised in that when carrying out high-temperature roasting activation, air speed is 1200
～2400h-1；Temperature is 360～450 DEG C.
7. according to the preparation method described in claim 2～6 any one, it is characterised in that described in time of being heated to reflux be 1
～24 hours, the described time continuing backflow is 1～24 hour, when refluxing total a length of 12～30 hours.
Preparation method the most according to claim 7, it is characterised in that described auxiliary agent is the compound containing molybdenio, contains
There is the compound of cerio or containing one or more in the compound of zirconio.
9. a preparation method for the maleic anhydride catalyst described in claim 1, including vanadic anhydride is placed in benzyl alcohol, isobutyl
The mixed liquor of alcohol and auxiliary agent composition is heated to reflux, adds phosphoric acid and continue backflow, then through solid-liquid separation, be dried, be pressed into
Maleic anhydride catalyst is obtained, it is characterised in that on the basis of vanadic anhydride quality after type and high-temperature roasting activation, each reactant
Mass ratio relation is vanadic anhydride: phosphoric acid: benzyl alcohol: isobutanol: auxiliary agent=1:(1.077～1.267): (0.01～
10): (0.813～10): (0.002～0.2).
Preparation method the most according to claim 9, it is characterised in that described high-temperature roasting activation be by water vapour,
The mixed gas of air and nitrogen composition is carried out, the volume ratio of water vapour, air and nitrogen in wherein said mixed gas
For 1:(0.1～1): (0.1～1)；
Preferably, when carrying out high-temperature roasting activation, air speed is 1200～2400h-1；Temperature is 360～450 DEG C.
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