CN109482211A - A kind of catalyst and preparation method thereof for synthesizing 2 cyano pyrazine - Google Patents
A kind of catalyst and preparation method thereof for synthesizing 2 cyano pyrazine Download PDFInfo
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- CN109482211A CN109482211A CN201710808835.3A CN201710808835A CN109482211A CN 109482211 A CN109482211 A CN 109482211A CN 201710808835 A CN201710808835 A CN 201710808835A CN 109482211 A CN109482211 A CN 109482211A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- PMSVVUSIPKHUMT-UHFFFAOYSA-N cyanopyrazine Chemical compound N#CC1=CN=CC=N1 PMSVVUSIPKHUMT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Natural products CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 26
- 229910000540 VOPO4 Inorganic materials 0.000 claims description 23
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 22
- 239000012266 salt solution Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 15
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 230000003292 diminished effect Effects 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 5
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000011964 heteropoly acid Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- -1 nitrogen-containing heterocycle aromatic nitriles Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910020881 PMo12O40 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- OTGFEQJKSRFOED-UHFFFAOYSA-N [P].[V].[Mo] Chemical compound [P].[V].[Mo] OTGFEQJKSRFOED-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002365 anti-tubercular Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IPEHBUMCGVEMRF-UHFFFAOYSA-N pyrazinecarboxamide Chemical class NC(=O)C1=CN=CC=N1 IPEHBUMCGVEMRF-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/28—Phosphorising
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having 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
- C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of catalyst and preparation method thereof for synthesizing 2 cyano pyrazine, in catalyst, the mass fraction of molybdenum is with MoO3It is calculated as 3%-30%, the mass fraction of vanadium is with V2O5It is calculated as 40%-55%, the mass fraction of phosphorus is with P2O5It is calculated as 25%-44%, the mass fraction of nitrogen is with NO2It is calculated as 0.75%-2.5%.The present invention also provides the preparation methods of above-mentioned catalyst.The features such as catalyst of the invention is used to have reactivity good at 2 cyano pyrazine 2- methylpyrazine gas phase ammonoxidation, and selectivity of product is high, high income, especially thermal stability are good, long service life.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of catalyst and its preparation for synthesizing 2 cyano pyrazine
Method.
Background technique
Cyanopyrazine and its derivative are more complex nitrogen-containing heterocycle aromatic nitriles, be important Organic Chemicals and
Intermediate.2 cyano pyrazine is the base stock for synthesizing the dedicated medicine of pyrazinamide class antituberculosis.The synthesis of 2 cyano pyrazine
There are many methods, wherein be currently preferred synthetic method with 2- methylpyrazine ammoxidation synthesis 2 cyano pyrazine, this technique
Key is to develop high conversion, highly selective catalyst.Forni et al. reports SbVMnO and VMoPO type ammoxidation catalysis
Agent, but yield is not high, most of 80% or so, up to 85%, reaction temperature is at 400 DEG C or more.
V2O5And vpo catalyst is a kind of solid catalyst with partial oxidation of alkanes function, while also being had preferable
Ammoxidation catalytic action, be used for gas phase ammonoxidation reaction have preferable effect.Patent CN 1408711A discloses one kind
The catalyst and synthetic method that 2- methylpyrazine synthesis 2 cyano pyrazine uses, the catalyst is prepared by infusion process
The loaded catalyst of VMoOP system, carrier are aluminium oxide or diamond dust, and the molecular proportion of active constituent V/P/Mo is 1/1-6/
0.01-1.It is calculated on the basis of catalytic amount 40g, 2- methylpyrazine intake is 0.05-2mL/min, and ammonia intake is
The intake of 100-200mL/min, air are 1000-2000mL/min, and the raw materials components mole ratio of raw material is 2- methylpyrazine/ammonia
Gas/air=1/8-20/10-90.The invention catalyst activity is high, the service life is long, does not need pot-life, and synthesis technology is easy, former
Expect high conversion rate, good product quality.But 2- methylpyrazine catalysis oxidation is synthesized into 2 cyano pyrazine, use vpo catalyst
Selectivity needs to be further improved.
In addition to this, polyoxometallate and some heteropoly compounds be also with low temperature ammoxidation performance, it is low
Warm catalytic ammoxidation reaction is better than vpo catalyst for the selectivity of target product.But due to the thermostabilization of heteropoly compound
Property is lower, limits it and is used for high temperature gas phase oxidation process.Patent CN102701944A is related to a kind of phosphorus molybdenum vanadium heteropolyacid catalysis
The method that oxidation 2- ethyl hexanal prepares 2 ethyl hexanoic acid, weighs phosphorus molybdenum vanadium heteropolyacid, is dissolved in distilled water, be re-dissolved in hydrochloric acid
In be configured to catalyst solution, in synthesis under normal pressure device, 2- ethyl hexanal and configured catalyst is added, slowly heating,
Stirring adjusts oxygen flow, starts to be passed through oxygen when temperature rises to reaction temperature, after reaction, isolate lower layer's water phase
Solution obtains the organic phase substance on upper layer, which is evaporated under reduced pressure, 2 ethyl hexanoic acid is obtained.The invention is logical
It crosses change catalyst molybdenum vanadium and when optimizes reaction condition, so that the conversion ratio of 2- ethyl hexanal reaches 99% or more, 2 ethyl hexanoic acid
Selectivity reach 98% or more, the yield of 2 ethyl hexanoic acid reaches 98% or more.But the catalytic process is liquid-phase oxidation process,
40-120 DEG C have good catalytic performance, but gas phase oxidation process temperature be higher than 300 DEG C, thermal stability become limitation because
Element.There are researchers to attempt to be carried on carrier (such as SiO2) its thermal stability is improved, however, since ammonium phosphomolybdate dissolves
Property is bad, and disperses loading process and do not allow easy operation control, so that this method is difficult to apply.
Based on the studies above it is recognized that while heteropllyacids compound has preferably activity and choosing for low temperature ammoxidation reaction
Selecting property, but its thermal stability difference becomes using problem, and in long-time high temperature, heteropoly acid skeleton structure is decomposed, Xiang Jie
Structure changes, and influences the using effect of catalyst.
Summary of the invention
In view of the deficiencies of the prior art, the catalyst and its preparation that the present invention provides a kind of for synthesizing 2 cyano pyrazine
Method.The catalyst thermal stability is good, for 2- methylpyrazine gas phase ammonoxidation at 2 cyano pyrazine, to be had reactivity
Well, the features such as selectivity of product is high, high income, especially thermal stability are good, long service life.
The catalyst that the present invention is used to synthesize 2 cyano pyrazine is ammonium phosphomolybdate-β-VOPO4Catalyst is in β-VOPO4's
On the basis of In-situ reaction heteropolyacid salt ammonium phosphomolybdate.In catalyst, the mass fraction of molybdenum is with MoO3It is calculated as 3%-30%, preferably 10%-
22%；The mass fraction of vanadium is with V2O5It is calculated as 40%-55%, preferably 45%-50%；The mass fraction of phosphorus is with P2O5It is calculated as 25%-44%, it is excellent
30%-40% is selected, the mass fraction of nitrogen is with NO2It is calculated as 0.75%-2.5%, preferably 1.25%-2%.
The present invention also provides above-mentioned for synthesizing the preparation method of the catalyst of 2 cyano pyrazine, including following content:
(1) by V2O5Certain time is reacted at a certain temperature with polar alcohol solvent, then phosphorus source is added into system and is reacted,
After the reaction was completed, through cooling, be filtered, washed, dry, obtain substance A；
(2) substance A is calcined into certain time in oxygen atmosphere, obtains substance B；
(3) dimolybdate salt solution is prepared, regulation system pH is 1-3, and substance B is placed in dimolybdate salt solution and is impregnated, and is filtered, and is done
Dry, calcining obtains catalyst.
In the present invention, polar alcohol solvent described in step (1) is propyl alcohol, isopropanol, butanol, isobutanol, benzyl alcohol, second two
One or more of alcohol, propylene glycol etc., preferably isobutanol.V2O5Proportion with polar alcohol solvent is 1g:5-30mL, preferably 1g:
8-15mL.Reaction temperature is 80-200 DEG C, reaction time 2-5h.
In the present invention, the phosphorus source that step (1) is added can be phosphoric acid, pyrophosphoric acid etc., and additional amount is to make phosphorus vanadium ratio 0.8-
1.5:1.It is added after phosphorus source in 80-200 DEG C of reaction 4-16h.
In the present invention, cooling described in step (1) can use natural cooling or accelerate cooling method at low temperature, cold
But to room temperature.Filter type can use natural filtration or be filtered under diminished pressure, and preferably be filtered under diminished pressure, vacuum degree 0.01-
0.1MPa.Washing can be rinsed using ethyl alcohol, acetone, isobutanol etc., to remove the soluble impurity of the surface of solids.It is dry
Temperature is 100-120 DEG C, drying time 10-12h.
In the present invention, the calcination temperature of step (2) is 500-700 DEG C, preferably 600-700 DEG C；Heating rate be 5-10 DEG C/
Min calcines 1-8h, preferably 4-6h in oxygen atmosphere, to obtain with β-VOPO4Substance B based on phase.
In the present invention, ammonium molybdate preparation is can be directly used in dimolybdate salt solution described in step (3), also can be used more
The molybdenum sources such as molybdate, sodium molybdate, molybdenum trioxide are reacted with ammonium salt to be made, and ammonium salt can be in ammonium nitrate, ammonium chloride, ammonium sulfate etc.
One or more, preferably directly use ammonium molybdate.The mass fraction for controlling dimolybdate salt solution is 1%-20%, preferably 5%-
15%.The pH for adjusting dimolybdate salt solution is 1-3, and the acid of use can be one or more of nitric acid, hydrochloric acid, sulfuric acid etc., excellent
Select nitric acid.
In the present invention, substance B is placed in dimolybdate salt solution by step (3) to be sufficiently impregnated, and controls ammonium molybdate and substance B
Mass ratio is (0.05-0.6): 1, preferably (0.1-0.25): 1, dip time 1-6h, preferably 2-3h.
In the present invention, the filtering of step (3) can use natural filtration or be filtered under diminished pressure, and preferably be filtered under diminished pressure, vacuum degree
For 0.01-0.09MPa.The filter cake of filtering is dried, drying temperature is 80-120 DEG C, drying time 5-12h；Calcining temperature
Degree is 400-600 DEG C, calcination time 3-6h.
Ammonium phosphomolybdate-β-VOPO of the present invention4The application of catalyst, using 2- methylpyrazine as raw material, using gas phase ammonoxidation
Reaction synthesis 2 cyano pyrazine；Wherein the molar ratio of 2- methylpyrazine, ammonia, air and deionized water is 1:(5-15): (10-
80): (3-20), preferably 1:(8-12): (25-50): (8-12)；Reaction temperature be 320-450 DEG C, preferably 350-420 DEG C, instead
It is 1-5h between seasonable.
Catalyst prepared by the present invention combines the common advantage of vpo catalyst and heteropolyacid salt catalyst, especially gram
The bad defect of heteropolyacid salt thermal stability has been taken, there is good using effect.It is being used for 2- methylpyrazine ammoxidation reaction
It prepares in the reaction of 2 cyano pyrazine, catalyst activity is obviously improved, and is improved the conversion ratio of 2- methylpyrazine, is improved simultaneously
The selectivity and yield of 2 cyano pyrazine product.Under optimum condition, the conversion ratio of 2- methylpyrazine is greater than 98%, 2- cyano pyrrole
Piperazine is selectively greater than 90%, and 2 cyano pyrazine yield is greater than 89%.In addition, the long-term operation stability of the catalyst also obtain it is bright
Aobvious to be promoted, significant change does not occur for the X ray diffracting characteristic peak of reaction front and back catalyst.
Detailed description of the invention
Fig. 1 is the XRD diagram of B substance prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD spectra of present invention reaction front and back catalyst.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Experimental method in following embodiment is unless otherwise specified conventional method in that art.Institute in following embodiments
Experimental material is commercially available from routine biochemistry reagent shop unless otherwise specified.
The crystal phase structure of catalyst of the present invention is surveyed using the D/max 2500X x ray diffractometer x of RIGAKU company, Japan
?.Catalyst elements content is measured by using the AXiosmAX ray fluorescence spectrometer of company, Dutch pa nanogram section.Pass through
Gas chromatograph analyzes reaction product and by-product, to calculate the concentration of wherein main component.Gas chromatograph uses
Agilent 7890A, chromatographic column are OV101(2m × 3mm i.d), 100 DEG C of column temperature, fid detector (250 DEG C).
2- methylpyrazine conversion ratio C calculation formula:
The calculation formula of 2 cyano pyrazine yield Y:
2 cyano pyrazine selectivity S calculation formula:
Embodiment 1
By 20g V2O53h is reacted at 109 DEG C with 300mL isobutanol, then adds 95% pyrophosphoric acid to make P:V=1.1 into system,
In 109 DEG C of reaction 12h after addition, after the reaction was completed, cooled to room temperature is filtered under diminished pressure reactant, and vacuum degree is
0.05 MPa.Then filter cake is washed using isobutanol, to remove the soluble impurity of the surface of solids.After washing,
110 DEG C drying 12 hours, obtain substance A.
Substance A is calcined under oxygen atmosphere, is warming up to 650 DEG C since room temperature with the rate of 5 DEG C/min, calcining
It 4 hours, is cooled to room temperature, obtains substance B.
Ammonium molybdate is used to prepare mass fraction as 10% dimolybdate salt solution, the pH using nitric acid control solution is 1.It will
10g substance B is added in the above-mentioned solution of 25g and is sufficiently impregnated, and impregnates 3 hours, is filtered under diminished pressure later, vacuum degree is
0.05 MPa, filter cake is 10 hours dry at 110 DEG C, it is calcined 5 hours at 450 DEG C, obtains ammonium phosphomolybdate-β-VOPO4Catalysis
Agent.The characteristic of catalyst is as shown in table 1.
Principal character peak in Fig. 1 is β-VOPO4The characteristic peak of structure, and the structure peak type is sharp, crystallinity is high, impurity
It is less.The principal character peak shown in Fig. 2 is phosphomolybdic acid ammonium salt (NH in catalyst4)3PMo12O40•4H2The characteristic peak of O, the peak
Mask β-VOPO4The characteristic peak of structure can be seen that by the comparison at reaction front and back catalyst characteristics peak anti-by high temperature
The Ying Hou, (NH of catalyst4)3PMo12O40•4H2O crystal phase structure does not change, it was demonstrated that catalyst structure at high temperature
Stablize, and there is excellent applied at elevated temperature performance.
Embodiment 2
By 20g V2O55h is reacted at 80 DEG C with 160mL isobutanol, 95% pyrophosphoric acid is then added into system makes P:V=0.8,
In 80 DEG C of reaction 5h after addition, after the reaction was completed, cooled to room temperature is filtered under diminished pressure reactant, and vacuum degree is
0.01MPa.Then filter cake is washed using isobutanol, to remove the soluble impurity of the surface of solids.After washing,
100 DEG C drying 12 hours, obtain substance A.
Substance A is calcined under oxygen atmosphere, is warming up to 500 DEG C since room temperature with the rate of 5 DEG C/min, calcining
It 6 hours, is cooled to room temperature, obtains substance B.
Ammonium molybdate is used to prepare mass fraction as 5% dimolybdate salt solution, the pH using nitric acid control solution is 3.It will
10g substance B is added in the above-mentioned solution of 10g and is sufficiently impregnated, and impregnates 3 hours, is filtered under diminished pressure later, vacuum degree is
0.01 MPa, filter cake is 12 hours dry at 100 DEG C, it is calcined 6 hours at 400 DEG C, obtains ammonium phosphomolybdate-β-VOPO4Catalysis
Agent.The characteristic of catalyst is as shown in table 1.
Embodiment 3
By 20g V2O5React 3h at 200 DEG C with 500mL isobutanol, then into system be added 95% pyrophosphoric acid make P:V=
1.5, in 200 DEG C of reaction 10h after addition, after the reaction was completed, cooled to room temperature is filtered under diminished pressure reactant, vacuum
Degree is 0.09MPa.Then filter cake is washed using isobutanol, to remove the soluble impurity of the surface of solids.After washing,
It is 10 hours dry at 120 DEG C, obtain substance A.
Substance A is calcined under oxygen atmosphere, is warming up to 700 DEG C since room temperature with the rate of 5 DEG C/min, calcining
It 3 hours, is cooled to room temperature, obtains substance B.
Ammonium molybdate is used to prepare mass fraction as 15% dimolybdate salt solution, the pH using nitric acid control solution is 2.It will
10g substance B is added in the above-mentioned solution of 40g and is sufficiently impregnated, and impregnates 3 hours, is filtered under diminished pressure later, vacuum degree is
0.09 MPa, filter cake is 6 hours dry at 120 DEG C, it is calcined 3 hours at 600 DEG C, obtains ammonium phosphomolybdate-β-VOPO4Catalysis
Agent.The characteristic of catalyst is as shown in table 1.
Embodiment 4
With embodiment 1, difference is for preparation process and condition: polar alcohol solvent is isopropanol, obtains ammonium phosphomolybdate-β-VOPO4
Catalyst.The characteristic of catalyst is as shown in table 1.
Embodiment 5
With embodiment 1, difference is for preparation process and condition: polar alcohol solvent is butanol, obtains ammonium phosphomolybdate-β-VOPO4It urges
Agent.The characteristic of catalyst is as shown in table 1.
Embodiment 6
With embodiment 1, difference is for preparation process and condition: polar alcohol solvent is ethylene glycol, obtains ammonium phosphomolybdate-β-VOPO4
Catalyst.The characteristic of catalyst is as shown in table 1.
Embodiment 7
With embodiment 1, difference is for preparation process and condition: polar alcohol solvent is propylene glycol, obtains ammonium phosphomolybdate-β-VOPO4
Catalyst.The characteristic of catalyst is as shown in table 1.
Embodiment 8
With embodiment 1, difference is for preparation process and condition: the phosphoric acid that the phosphorus source of addition is 85% obtains ammonium phosphomolybdate-β-
VOPO4Catalyst.The characteristic of catalyst is as shown in table 1.
Embodiment 9
With embodiment 1, difference is for preparation process and condition: the dimolybdate salt solution of use using sodium molybdate with ammonium salt the system of reacting
, ammonium salt is ammonium nitrate, and the mass fraction of control dimolybdate salt solution is 10%, obtains ammonium phosphomolybdate-β-VOPO4Catalyst.It urges
The characteristic of agent is as shown in table 1.
Embodiment 10
With embodiment 1, difference is for preparation process and condition: the dimolybdate salt solution of use is reacted using molybdenum trioxide with ammonium salt
It is made, ammonium salt is ammonium sulfate, and the mass fraction of control dimolybdate salt solution is 10%, obtains ammonium phosphomolybdate-β-VOPO4Catalyst.
The characteristic of catalyst is as shown in table 1.
Embodiment 11
With embodiment 1, difference is for preparation process and condition: adjusting the pH of dimolybdate salt solution using hydrochloric acid, obtains phosphomolybdic acid
Ammonium-β-VOPO4Catalyst.The characteristic of catalyst is as shown in table 1.
Embodiment 12
With embodiment 1, difference is for preparation process and condition: being changed to natural filtration for being filtered under diminished pressure, obtains ammonium phosphomolybdate-β-
VOPO4Catalyst.The characteristic of catalyst is as shown in table 1.
Comparative example 1
With embodiment 1, difference is for preparation process and condition: alcoholic solvent uses ethyl alcohol, obtains ammonium phosphomolybdate-β-VOPO4Catalysis
Agent.The characteristic of catalyst is as shown in table 1.
Comparative example 2
With embodiment 1, difference is for preparation process and condition: substance A is placed directly in dimolybdate salt solution without calcining,
Obtain ammonium phosphomolybdate-β-VOPO4Catalyst.The characteristic of catalyst is as shown in table 1.
Comparative example 3
Preparation process and condition are with embodiment 1, and difference is: substance A is calcined in atmosphere of inert gases, obtain ammonium phosphomolybdate-
β-VOPO4Catalyst.The characteristic of catalyst is as shown in table 1.
Comparative example 4
With embodiment 1, difference is for preparation process and condition: the pH for adjusting dimolybdate salt solution is 4, obtains ammonium phosphomolybdate-β-
VOPO4Catalyst.The characteristic of catalyst is as shown in table 1.
Table 1
Evaluating catalyst:
By Catalyst packing in fixed bed reactors, raw material 2- methylpyrazine and deionized water are matched according to the molar ratio of 1:10
2- methylpyrazine solution is made, guarantee liquid feed air speed is 0.3h-1, while it being passed through the mixed gas of ammonia and air, so that
2- methylpyrazine: ammonia: air: the molar ratio of deionized water is 1:10:30:10, and reaction temperature is 380 DEG C, and reaction pressure is normal
Pressure, reaction started sampling analysis after 2 hours, and the results are shown in Table 2.
Table 2
As can be seen from Table 2, according to method described in the invention, the catalyst prepared is reached in methylpyrazine conversion ratio
When to 90% or more, 85% or more selectively can achieve, the yield of cyanopyrazine reaches 80% or more.And it is described in comparative example
Method preparation catalyst in due to ammonium phosphomolybdate and β-VOPO4Good interaction can not be formed, ammonium phosphomolybdate is caused
Thermal stability is poor during the reaction, selectively has an adverse effect to methylpyrazine conversion ratio and cyanopyrazine, causes
Final product yield decline.
Claims (14)
1. a kind of for synthesizing the catalyst of 2 cyano pyrazine, it is characterised in that the catalyst is ammonium phosphomolybdate-β-VOPO4Catalysis
Agent, in catalyst, the mass fraction of molybdenum is with MoO3It is calculated as 3%-30%, the mass fraction of vanadium is with V2O5It is calculated as 40%-55%, the matter of phosphorus
Score is measured with P2O5It is calculated as 25%-44%, the mass fraction of nitrogen is with NO2It is calculated as 0.75%-2.5%.
2. a kind of preparation method of catalyst described in claim 1, it is characterised in that including following content:
(1) by V2O5Certain time is reacted at a certain temperature with polar alcohol solvent, then phosphorus source is added into system and is reacted,
After the reaction was completed, through cooling, be filtered, washed, dry, obtain substance A；
(2) substance A is calcined into certain time in oxygen atmosphere, obtains substance B；
(3) dimolybdate salt solution is prepared, regulation system pH is 1-3, and substance B is placed in dimolybdate salt solution and is impregnated, and is filtered, and is done
Dry, calcining obtains catalyst.
3. according to the method described in claim 2, it is characterized by: polar alcohol solvent described in step (1) is propyl alcohol, isopropyl
One or more of alcohol, butanol, isobutanol, benzyl alcohol, ethylene glycol, propylene glycol etc..
4. according to the method in claim 2 or 3, it is characterised in that: step (1) described V2O5With the proportion of polar alcohol solvent
For 1g:5-30mL.
5. according to the method described in claim 2, it is characterized by: reaction temperature described in step (1) be 80-200 DEG C, reaction
Time is 2-5h.
6. according to the method described in claim 2, it is characterized by: the phosphorus source that step (1) is added is phosphoric acid or pyrophosphoric acid, addition
Amount is to make phosphorus vanadium ratio 0.8-1.5:1.
7. according to the method described in claim 2, it is characterized by: step (1) is added after phosphorus source in 80-200 DEG C of reaction 4-
16h。
8. according to the method described in claim 2, it is characterized by: cooling described in step (1) is using natural cooling or low
Temperature is lower to accelerate cooling method, is cooled to room temperature；Filtering is using natural filtration or is filtered under diminished pressure；Washing using ethyl alcohol, acetone or
Isobutanol is rinsed；Drying temperature is 100-120 DEG C, drying time 10-12h.
9. according to the method described in claim 2, heating is fast it is characterized by: the calcination temperature of step (2) is 500-700 DEG C
Rate is 5-10 DEG C/min, calcines 1-8h in oxygen atmosphere.
10. according to the method described in claim 2, it is characterized by: dimolybdate salt solution described in step (3) directlys adopt molybdenum
Sour ammonium is prepared, or reacts obtained with ammonium salt using polymolybdote, sodium molybdate or molybdenum trioxide, ammonium salt be ammonium nitrate, ammonium chloride,
One or more of ammonium sulfate etc., the mass fraction of control dimolybdate salt solution are 1%-20%.
11. the method according to claim 2 or 10, it is characterised in that: the pH that step (3) adjusts dimolybdate salt solution is used
One or more of nitric acid, hydrochloric acid, sulfuric acid etc..
12. according to the method described in claim 2, it is characterized by: substance B is placed in dimolybdate salt solution and fills by step (3)
Sub-dip stain, the mass ratio for controlling ammonium molybdate and substance B is (0.1-0.6): 1, preferably (0.1-0.25): 1, dip time 1-
6h, preferably 2-3h.
13. according to the method described in claim 2, it is characterized by: the filtering of step (3) is using natural filtration or depressurizes
Filter；The filter cake of filtering is dried, drying temperature is 80-120 DEG C, drying time 5-12h；Calcination temperature is 400-600
DEG C, calcination time 3-6h.
14. the application of catalyst described in claim 1, it is characterised in that: using 2- methylpyrazine as raw material, using gas phase ammonoxidation
Reaction synthesis 2 cyano pyrazine, 2- methylpyrazine, ammonia, air and deionized water molar ratio be 1:(5-15): (10-80):
(3-20), reaction temperature are 320-450 DEG C, reaction time 1-5h.
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