CN105233849A - Composite catalyst used for synthesis of 3-cyanopyridine, and preparation method and application thereof - Google Patents
Composite catalyst used for synthesis of 3-cyanopyridine, and preparation method and application thereof Download PDFInfo
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- CN105233849A CN105233849A CN201510607257.8A CN201510607257A CN105233849A CN 105233849 A CN105233849 A CN 105233849A CN 201510607257 A CN201510607257 A CN 201510607257A CN 105233849 A CN105233849 A CN 105233849A
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- nicotinonitrile
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- chloride
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- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 70
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000013543 active substance Substances 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 25
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 24
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 24
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 24
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 19
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 84
- 239000011149 active material Substances 0.000 claims description 54
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 38
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000741 silica gel Substances 0.000 claims description 25
- 229910002027 silica gel Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- 239000011780 sodium chloride Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 47
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 239000000376 reactant Substances 0.000 description 9
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000011260 aqueous acid Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 235000001968 nicotinic acid Nutrition 0.000 description 3
- 239000011664 nicotinic acid Substances 0.000 description 3
- 229960003512 nicotinic acid Drugs 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000005152 nicotinamide Nutrition 0.000 description 2
- 239000011570 nicotinamide Substances 0.000 description 2
- 229960003966 nicotinamide Drugs 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alkyl pyridine Chemical compound 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010641 nitrile hydrolysis reaction Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a composite catalyst used for synthesis of 3-cyanopyridine, and a preparation method and application thereof. The composite catalyst used for synthesis of 3-cyanopyridine is characterized by comprising main active substances and auxiliary active substances, wherein the main active substances comprise Cr2O3 and V2O5, or also comprise ammonium molybdate, and an atomic molar ratio of V to ammonium molybdate to Cr is 1: 0.09-0.85: 0.2-1.0; and the auxiliary active substances are a mixture of (1) oxide or chloride of P, (2) oxide or chloride of at least one selected from the group consisting of Ni and Bi, wherein the oxide or the chloride of Ni and Bi are mixed in any ratio, and (3) oxide or chloride of at least one selected from the group consisting of K, Na and CS, wherein two or three oxides or chlorides of K, Na and CS are mixed in any ratio, and an atomic ratio of V to Ni to Bi to P to Na, K or/and Cs is 1: 0.0018-0.81: 0.0018-0.81: 0.0018-0.81: 0.003-0.1. By using the catalyst provided by the invention, high selectivity and high conversion rate are obtained; and the catalyst has long service life and low mole content of ammonia.
Description
Technical field
The present invention relates to a kind of composite catalyst for the synthesis of nicotinonitrile and its preparation method and application.
Background technology
Nicotinonitrile has another name called nicotinic acid nitrile, is a kind of important medicine intermediate.Such as: nicotinic acid nitrile hydrolysis can obtain niacinamide and nicotinic acid.Niacinamide and nicotinic acid are the one of Cobastab, extensive use in the industries such as food, medicine and feed addictive.Nicotinic acid can obtain from 3-picoline through gaseous oxidation, but easily generates V-pyridine oxide, so the path of yield ratio gas phase ammonoxidation is much lower because of during oxidation.Gas phase ammonoxidation synthesis nicotinic acid nitrile, both at home and abroad existing bibliographical information, but the yield of domestic production is up to now very low, only has about 6%.3-picoline oxidative synthesis nicotinonitrile, mostly is patent document abroad.The catalyst that Degussa company prepares for main active material with the oxide of V and Sb, catalyst preparation process is complicated, and ammonia consumption is large, the low conversion rate (US4447612) of alkyl pyridine.The catalyst that Lummus Inc. is standby, the poor selectivity (only having 89.7%) of nicotinic acid nitrile, conversion ratio too low (being only 51%) (US4284781).Mitsubishi gas chemical company to decide catalyst activity and selectivity all lower (US4963687) prepared by active material with the oxide of V, Cr and B.The catalyst using Ti and V as main active material prepared of catalyst chemical industrial company of Japan, select purity to be that the sintered silicon carbon of 98-99% makes carrier, Catalyst Production cost is higher, and nicotinic acid nitrile yield also lower (JP74-34673).The catalyst 3-picoline being main active constituent with Sb and V and Fe that US6392048 document is introduced: oxygen: peace=1:12.1:3.5 (amount of substance ratio), react under the condition of 643K, nicotinonitrile molar yield be 87%, US6107510 patent document introduce with Cr, V, B and M.Be the catalyst of main active material, react under 663K condition, molar product yield is 93.3%, 3-picoline conversion ratio is 93.6%.Can find out from above patent document, the ammoxidation of 3-picoline synthesis nicotinonitrile, the conversion ratio of raw material and the molar yield of product all lower, production cost is higher.Therefore, developing a kind of selective good, efficient catalyst that yield is high and suitable process conditions, comparatively low production cost, is the key technical problem of gas phase ammonoxidation synthesis nicotinic acid nitrile.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide a kind of composite catalyst for the synthesis of nicotinonitrile and its preparation method and application, adopt this catalyst, selective good, conversion ratio is high; Catalyst long service life, the amount of substance of ammonia is smaller.
For achieving the above object, the technical solution adopted in the present invention is: a kind of composite catalyst for the synthesis of nicotinonitrile, is characterized in that, comprises main active material and auxiliary active agent; Adopt r-Al
2o
3or spherical silica gel makes carrier;
Main active material comprises Cr
2o
3and V
2o
5, or add ammonium molybdate again, the mol ratio of its atom is V (V
2o
5): M
0(the M in ammonium molybdate
0): Cr (Cr
2o
3in Cr)=1:0.09 ~ 0.85:0.2 ~ 1.0; Auxiliary active agent is the mixture of following three kinds: the 1. oxide of P or chloride, 2. at least one oxide in Ni, Bi or chloride, be any proportioning when the oxide of Ni, Bi or chloride mixing, 3. at least one oxide in K, Na, Cs or chloride, wherein, be any proportioning when two kinds in K, Na, Cs or three kinds of oxides or chloride mixing; Its atomic ratio is V:Ni:Bi:P:Na, K or/and (note: V is V in main active material in Cs=1:0.0018 ~ 0.81:0.0018 ~ 0.81:0.0018 ~ 0.81:0.003 ~ 0.1
2o
5v).
The mass content of the active constituent in main active material and auxiliary active agent is that 1 ~ 31%[is preferably 3-16% (Wt)].
Spherical silica gel adopts 50-120 object spherical silica gel.
By above-mentioned skill scheme, main active material the best is Cr
2o
3, V
2o
5, Cr
2o
31.20 ~ 1.22 grams, V
2o
53.38 gram; Auxiliary active agent the best is P
2o
5, BiCl
3, NiCl
26H
2one in O and KCl, NaCl, CsCl, P
2o
51.10 ~ 1.25 grams, BiCl
30.40 ~ 0.43 gram, NiCl
26H
2o2.40 ~ 2.62 gram, KCl (or NaCl or CsCl) 0.19 ~ 0.22 gram.
The preparation method of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, is characterized in that, comprise the steps:
1) press, main active material comprises Cr
2o
3and V
2o
5, or add ammonium molybdate again, the mol ratio of its atom is V (V
2o
5in V): M
0(the M in ammonium molybdate
0): Cr (Cr
2o
3in Cr)=1:0.09 ~ 0.85:0.2 ~ 1.0; Auxiliary active agent is the mixture of following three kinds: the 1. oxide of P or chloride, 2. at least one oxide in Ni, Bi or chloride, be any proportioning when the oxide of Ni, Bi or chloride mixing, 3. at least one oxide in K, Na, Cs or chloride, wherein, be any proportioning when two kinds in K, Na, Cs or three kinds of oxides or chloride mixing; Its atomic ratio is V:Ni:Bi:P:Na, K or/and (note: V is V in main active material in Cs=1:0.0018 ~ 0.81:0.0018 ~ 0.81:0.0018 ~ 0.81:0.003 ~ 0.1
2o
5v); Choose the raw material of main active material and auxiliary active agent;
2) main active material and auxiliary active agent being dissolved (solvent is for containing careless aqueous acid), obtaining mixed solution (V
2o
53.38 grams: 220 ml distilled waters containing 17 grams of oxalic acid); Adopt r-Al
2o
3or spherical silica gel makes carrier, then carrier (burnt or dry carrier) is poured in above-mentioned mixed solution, make it just to be submerged, stir [or after stirring, again through ageing (ageing 20 hours), oven dry], 773K (499.85 DEG C) activation 6 hours, namely obtain the composite catalyst for the synthesis of nicotinonitrile.
The raw material synthesizing composite catalyst of the present invention main active material used and auxiliary active agent is organic salt, inorganic salts, oxide etc.Conventional organic salt has oxalates, acetate, vinic acid salt; Inorganic salts have nitrate, carbonate, phosphate, ammonium salt and chloride etc.
By technique scheme, preferred plan: a kind of preparation method of the composite catalyst for the synthesis of nicotinonitrile, is characterized in that, comprise the steps:
1) press, main active material the best is Cr
2o
3, V
2o
5and ammonium molybdate, Cr
2o
31.20 ~ 1.22 grams, V
2o
53.38 grams, ammonium molybdate 0.90 gram ~ 1.06 grams; Auxiliary active agent the best is P
2o
5, BiCl
3, NiCl
26H
2one in O and KCl, NaCl, CsCl, P
2o
51.10 ~ 1.25 grams, BiCl
30.40 ~ 0.43 gram, NiCl
26H
2o2.40 ~ 2.62 gram, KCl or NaCl or CsCl0.19 ~ 0.22 gram; Choose raw material;
2) by V
2o
5and Cr
2o
3join together in 220 ml distilled waters containing 17 grams of oxalic acid, in 353K heating for dissolving, make solution A; P is added again in this solution A
2o
5, BiCl
3, ammonium molybdate, NiCl
26H
2one in O and KCl, NaCl, CsCl, stirs, makes active substance solution B; By r-Al
2o
3or spherical silica gel 95 grams joins in solution B, make it just to be submerged, stir, after 378K is dried, then activate 6 hours under 773K, obtain the composite catalyst for the synthesis of nicotinonitrile.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, it is characterized in that, comprises the steps:
1) add the composite catalyst for the synthesis of nicotinonitrile in the reactor, be warming up to 613K ~ 703K (reaction temperature); Composite catalyst is 80 grams, and 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours;
2) by 3-picoline: ammonia: the oxygen (oxygen in air, by air conversion): 3-picoline, ammonia, air and water vapour (reactant mixture), than being=1:1.2 ~ 5:7 ~ 14:1 ~ 15, are sent in reactor that [space velocity of reaction is 600 ~ 1100h by the amount of substance of water vapour
-1], obtain nicotinonitrile.
The ammoxidation reaction of 3-picoline can carry out in a fluidized bed reactor, also can carry out in fixed bed reactors.The quartz ampoule that the reactor that the present invention uses is internal diameter 33 millimeters, urges the loadings of compound agent to be 0.06-0.12 liter by long 400 millimeters.Reactor outside electric-heating-wire-heating, the bed temperature thermocouple measurement of reactor.
In the material mixed gas entering reactor, make diluent with water vapour, replace purity oxygen with air.
React the ammonia amount used, exceed theoretical amount.During because using a large amount of ammonia, need to reclaim unreacted ammonia, therefore preferred ammonia amount is 1.9 ~ 2.8 times of theoretical amount.In material gas mixture, the amount of oxygen is at least 7 times of theoretical amount, is preferably 10 ~ 12 times of theoretical amount.
Reaction temperature is 613K ~ 703K, and during lower than 613K, the conversion ratio of raw material is lower, and during higher than 703K, can cause deep oxidation, causes nicotinonitrile yield lower.Preferred reaction temperature is 633K ~ 663K.
This reaction is carried out at ambient pressure, also can slightly higher than or lower than the condition of normal pressure under carry out.
The product reclaiming reaction from this reaction mixture gas can adopt common method.The temperature that reaction mixture gas directly can be cooled to product become solid to separate out, to reclaim product wherein.
Compared with the prior art, the invention has the beneficial effects as follows: adopt catalyst provided by the present invention and corresponding method for ammoxidation, product yield is all higher with selection, and the conversion ratio of raw material is higher, and the amount of substance of ammonia, than little, can reduce production cost.So this technology has good using value.
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
For the synthesis of a composite catalyst for nicotinonitrile, comprise main active material and auxiliary active agent; Spherical silica gel is adopted to make carrier.Main active material is Cr
2o
3, V
2o
5and ammonium molybdate, Cr
2o
31.20 grams, V
2o
53.38 grams, ammonium molybdate 1.06 grams.Auxiliary active agent is P
2o
5, KCl, BiCl
3, NiCl
26H
2o, P
2o
51.25 grams, KCl0.21 gram, BiCl
30.43 gram, NiCl
26H
2o2.62 gram.
The preparation method of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, comprises the steps: 3.38 grams of V
2o
5with 1.20 grams of Cr
2o
3join together in 220 ml distilled waters containing 17 grams of oxalic acid, in about 353K heating for dissolving, make blue solution; The P of 1.25 grams is added again in this solution
2o
5with 0.21 gram of KCl, the BiCl of 0.43 gram
3, the ammonium molybdate [(NH of 1.06 grams
4) 6M
o7o
244H
2o], the NiCl of 2.62 grams
26H
2o, stirs, makes the solution of active material.The spherical silica gel 95 grams (Qingdao Marine Chemical Co., Ltd.) of drying is joined in the solution of above-mentioned active material, make it just to be submerged, stir, after 378K is dried, under 773K, activate 6 hours again, obtain the composite catalyst for the synthesis of nicotinonitrile.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, comprise the steps: that at internal diameter be in the quartz tube reactor of 33 millimeters, add by the obtained composite catalyst 80 grams of method described in the present embodiment, be warming up to 643K; 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours; By 3-picoline: ammonia: oxygen (oxygen in air, by air conversion): the amount of substance of water vapour=1:1.9:9:4 sends into reactor than by reactant mixture, and (space velocity of reaction is 600 ~ 1100h
-1), obtain nicotinonitrile.The conversion ratio of 3-picoline is 99.4%, and the molar yield of nicotinonitrile is 99.1%.
Embodiment 2:
For the synthesis of a composite catalyst for nicotinonitrile, comprise main active material and auxiliary active agent; Spherical silica gel is adopted to make carrier.Main active material is Cr
2o
3, V
2o
5and ammonium molybdate, Cr
2o
31.20 grams, V
2o
53.38 grams, ammonium molybdate 1.00 grams.Auxiliary active agent is P
2o
5, NaCl, BiCl
3, NiCl
26H
2o, P
2o
51.10 grams, NaCl0.19 gram, BiCl
30.40 gram, NiCl
26H
2o2.40 gram.
The preparation method of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, comprises the steps: 3.38 grams of V
2o
5with 1.20 grams of Cr
2o
3join together in 220 ml distilled waters containing 17 grams of oxalic acid, in about 353K heating for dissolving, make blue solution; And then in this solution, add the ammonium molybdate [(NH of 1.00 grams
4) 6M
o7o
244H
2o], the P of 1.10 grams
2o
5, 0.19 gram of NaCl and 2.40 gram NiCl
26H
2o, 0.40 gram of BiCl
3be uniformly dissolved, make clear solution.Join in solution by the spherical silica gel 95 grams (Qingdao Marine Chemical Co., Ltd.) of drying, make it just to be submerged, stir, 378K is dried, then activates 6 hours under 773K, obtains the required composite catalyst for the synthesis of nicotinonitrile.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, comprise the steps: that at internal diameter be in the quartz tube reactor of 33 millimeters, add by the obtained composite catalyst 80 grams of method described in the present embodiment, maintain reaction bed temperature at 643K; 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours; By 3-picoline: ammonia: the oxygen in air: the amount of substance of water vapour=1:1.9:9:4 sends into than by reactant mixture in reactor that (space velocity of reaction is 600 ~ 1100h
-1), obtain nicotinonitrile.The conversion ratio of 3-picoline is 98.8%, and the molar yield of nicotinonitrile is 96.8%.
Embodiment 3:
For the synthesis of a composite catalyst for nicotinonitrile, comprise main active material and auxiliary active agent; Adopt r-Al
2o
3or spherical silica gel makes carrier.Main active material is Cr
2o
3, V
2o
5and ammonium molybdate, Cr
2o
31.22 grams, V
2o
53.38 grams of ammonium molybdates 0.90 gram.Auxiliary active agent is P
2o
5, NaCl, BiCl
3, NiCl
26H
2o, P
2o
51.10 grams, NaCl0.19 gram, BiCl
30.40 gram, NiCl
26H
2o2.60 gram.
The preparation method of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, comprises the steps: 3.38 grams of V
2o
5with 1.22 grams of Cr
2o
3join together in 220 ml distilled waters containing 17 grams of oxalic acid, in about 353K heating for dissolving, make solution A; And then in this solution, add the ammonium molybdate [(NH of 0.90 gram
4) 6M
o7o
244H
2o], the P of 1.10 grams
2o
5, 0.19 gram of NaCl and 2.60 gram NiCl
26H
2o, 0.40 gram of BiCl
3be uniformly dissolved, make solution B.Join in solution B by the spherical silica gel 95 grams (Qingdao Marine Chemical Co., Ltd.) of drying, make it just to be submerged, stir, 378K is dried, then activates 6 hours under 773K, obtains the required composite catalyst for the synthesis of nicotinonitrile.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, comprise the steps: that at internal diameter be in the quartz tube reactor of 33 millimeters, add by the obtained composite catalyst 80 grams of method described in the present embodiment, maintain reaction bed temperature at 643K; 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours; By 3-picoline: ammonia: the oxygen in air: the amount of substance of water vapour=1:2:9:4 is sent in reactor than by reactant mixture, the space velocity of reaction is 600 ~ 1100h
-1, obtain nicotinonitrile.The conversion ratio of 3-picoline is 98.9%, and the molar yield of nicotinonitrile is 97.8%.
Embodiment 4:
Replace the NaCl in embodiment 2 with 0.22 gram of CsCl, method for preparing catalyst is with embodiment 2.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, comprise the steps: that at internal diameter be in the quartz tube reactor of 33 millimeters, add by the obtained composite catalyst 80 grams of method described in the present embodiment, maintain reaction bed temperature at 643K; 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours; By 3-picoline: ammonia: the oxygen in air: the amount of substance of water vapour=1:2:9:4 is sent in reactor than by reactant mixture, the space velocity of reaction is 600 ~ 1100h
-1, obtain nicotinonitrile.The conversion ratio of 3-picoline is 98.8%, and the molar yield of nicotinonitrile is 97.7%.
Embodiment 5:
Catalyst preparing: use catalyst carrier instead r-Al
2o
3, all the other are with embodiment 1, and press the method Kaolinite Preparation of Catalyst of embodiment 1.
Prepare nicotinonitrile: in the reactor of embodiment 1, carry out ammoxidation by the reaction condition of embodiment 1, the molar yield of nicotinonitrile is the conversion ratio of 94.8%, 3-picoline is 98.3%.
Embodiment 6:
Catalyst preparing: use catalyst carrier instead r-Al
2o
3, all the other amount of substances completely with embodiment 2, and press the method Kaolinite Preparation of Catalyst of embodiment 2.
Prepare nicotinonitrile: in the reactor of embodiment 2, carry out ammoxidation by the reaction condition of embodiment 2, the conversion ratio of 3-picoline is 96.6%, and the molar yield of nicotinonitrile is 94.9%.
Embodiment 7:
For the synthesis of a composite catalyst for nicotinonitrile, comprise main active material and auxiliary active agent; Adopt r-Al
2o
3or spherical silica gel makes carrier.Main active material is Cr
2o
3, V
2o
5, the mol ratio of its atom is V:Cr=1::0.2.Auxiliary active agent is P
2o
5, KCl, BiCl
3, NiCl
26H
2o, its atomic ratio is that (note: V is V in main active material to V:Ni:Bi:P:K=1:0.0018:0.0018:0.0018:0.003
2o
5v).
The preparation method of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, comprises the steps: 1) by said ratio, choose the raw material of main active material and auxiliary active agent; 2) main active material and auxiliary active agent being dissolved (solvent is for containing careless aqueous acid), obtaining solution (V
2o
53.38 grams: 220 ml distilled waters containing 17 grams of oxalic acid); Adopt r-Al
2o
3make carrier, then carrier is poured in above-mentioned solution, make it just to be submerged, then after ageing (ageing 6 hours hours), drying, 773K (499.85 DEG C) activation 6 hours, namely obtain the composite catalyst for the synthesis of nicotinonitrile.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, comprises the steps:
1) add the composite catalyst for the synthesis of nicotinonitrile in the reactor, be warming up to 613K (reaction temperature); Composite catalyst 80 grams, 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours;
2) by 3-picoline: ammonia: oxygen in air (by air conversion): 3-picoline, ammonia, air and water vapour (reactant mixture), than being=1:1.2:7:1, are sent in reactor that [space velocity of reaction is 600h by the amount of substance of water vapour
-1], obtain nicotinonitrile.
The conversion ratio of 3-picoline is 96.7%, and the molar yield of nicotinonitrile is 95.1%.
Embodiment 8:
For the synthesis of a composite catalyst for nicotinonitrile, comprise main active material and auxiliary active agent; Adopt r-Al
2o
3or spherical silica gel makes carrier.Main active material is Cr
2o
3, V
2o
5, the mol ratio of its atom is V:Cr=1::1.0.Auxiliary active agent is P
2o
5, KCl, BiCl
3, NiCl
26H
2o, its atomic ratio is that (note: V is V in main active material to V:Ni:Bi:P:K=1:0.81:0.81:0.81:0.1
2o
5v).
The preparation method of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, comprises the steps: 1) by said ratio, choose the raw material of main active material and auxiliary active agent; 2) main active material and auxiliary active agent being dissolved (solvent is for containing careless aqueous acid), obtaining solution (V
2o
53.38 grams: 220 ml distilled waters containing 17 grams of oxalic acid); Adopt r-Al
2o
3make carrier, then carrier (burnt or dry carrier) is poured in above-mentioned solution, make it just to be submerged, again after ageing (ageing 6 hours hours), drying, 773K (499.85 DEG C) activation 6 hours, namely obtain the composite catalyst for the synthesis of nicotinonitrile.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, comprises the steps:
1) add the composite catalyst for the synthesis of nicotinonitrile in the reactor, be warming up to 703K (reaction temperature); Composite catalyst 80 grams, 3-picoline adopts continuous feed, and charging is by 5 ~ 8 Grams Per Hours;
2) by 3-picoline: ammonia: oxygen in air (by air conversion): 3-picoline, ammonia, air and water vapour (reactant mixture), than being=1:1.5:14:15, are sent in reactor that [space velocity of reaction is 1100h by the amount of substance of water vapour
-1], obtain nicotinonitrile.
The conversion ratio of 3-picoline is 96.8%, and the molar yield of nicotinonitrile is 95.8%.
Embodiment 9:
For the synthesis of a composite catalyst for nicotinonitrile, comprise main active material and auxiliary active agent; Spherical silica gel is adopted to make carrier;
Main active material comprises Cr
2o
3and V
2o
5, the mol ratio of its atom is V (V
2o
5): Cr (Cr
2o
3)=1:0.2; Auxiliary active agent is the mixture of following three kinds: 1. P
2o
5, 2. NiCl
2, 3. NaCl; Its atomic ratio is V:Ni:P:Na, (note: V is V in main active material to=1:0.0018:0.0018:0.003
2o
5v).
Spherical silica gel adopts 50-120 object spherical silica gel.
The preparation method of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, comprises the steps:
1) press, main active material comprises Cr
2o
3and V
2o
5, the mol ratio of its atom is V (V
2o
5): Cr (Cr
2o
3)=1:0.2; Auxiliary active agent is the mixture of following three kinds: 1. P
2o
5, 2. NiCl
2, 3. NaCl; Its atomic ratio is V:Ni:P:Na, (note: V is V in main active material to=1:0.0018:0.0018:0.003
2o
5v); Choose the raw material of main active material and auxiliary active agent;
2) main active material and auxiliary active agent being dissolved (solvent is for containing careless aqueous acid), obtaining mixed solution (V
2o
53.38 grams: 220 ml distilled waters containing 17 grams of oxalic acid); Spherical silica gel is adopted to make carrier, then carrier is poured in above-mentioned mixed solution, make it just to be submerged, stir [or after stirring, again through ageing (ageing 20 hours), oven dry], 773K (499.85 DEG C) activation 6 hours, namely obtain the composite catalyst for the synthesis of nicotinonitrile.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, comprises the steps:
1) add the composite catalyst for the synthesis of nicotinonitrile in the reactor, be warming up to 613K ~ 703K (reaction temperature); Composite catalyst is 80 grams, and 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours;
2) by 3-picoline: ammonia: the oxygen (oxygen in air, by air conversion): the amount of substance of water vapour is than being=1:1.2:7:1,3-picoline, ammonia, air and water vapour (reactant mixture) are sent in reactor, obtains nicotinonitrile.
The conversion ratio of 3-picoline is 96.7%, and the molar yield of nicotinonitrile is 95.7%.
Embodiment 10:
For the synthesis of a composite catalyst for nicotinonitrile, comprise main active material and auxiliary active agent; Spherical silica gel is adopted to make carrier;
Main active material comprises Cr
2o
3and V
2o
5, the mol ratio of its atom is V (V
2o
5): Cr (Cr
2o
3)=1:1.0; Auxiliary active agent is the mixture of following three kinds: 1. P
2o
5, 2. BiCl
3, 3. NaCl; Its atomic ratio is V:Bi:P:Na, (note: V is V in main active material to=1:0.81:0.81:0.1
2o
5v).
Spherical silica gel adopts 50-120 object spherical silica gel.
The preparation method of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, comprises the steps:
1) press, main active material comprises Cr
2o
3and V
2o
5, the mol ratio of its atom is V (V
2o
5): Cr (Cr
2o
3)=1:1.0; Auxiliary active agent is the mixture of following three kinds: 1. P
2o
5, 2. BiCl
3, 3. NaCl; Its atomic ratio is V:Bi:P:Na, (note: V is V in main active material to=1:0.81:0.81:0.1
2o
5v); Choose the raw material of main active material and auxiliary active agent;
2) main active material and auxiliary active agent being dissolved (solvent is for containing careless aqueous acid), obtaining mixed solution (V
2o
53.38 grams: 220 ml distilled waters containing 17 grams of oxalic acid); Spherical silica gel is adopted to make carrier, then carrier is poured in above-mentioned mixed solution, make it just to be submerged, stir [or after stirring, again through ageing (ageing 20 hours), oven dry], 773K (499.85 DEG C) activation 6 hours, namely obtain the composite catalyst for the synthesis of nicotinonitrile.
The application of above-mentioned a kind of composite catalyst for the synthesis of nicotinonitrile, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, comprises the steps:
1) add the composite catalyst for the synthesis of nicotinonitrile in the reactor, be warming up to 613K ~ 703K (reaction temperature); Composite catalyst is 80 grams, and 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours;
2) by 3-picoline: ammonia: the oxygen (oxygen in air, by air conversion): 3-picoline, ammonia, air and water vapour (reactant mixture), than being=1:5:14:15, are sent in reactor that [space velocity of reaction is 600 ~ 1100h by the amount of substance of water vapour
-1], obtain nicotinonitrile.
The conversion ratio of 3-picoline is 96.7%, and the molar yield of nicotinonitrile is 95.7%.
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of technological parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (7)
1. for the synthesis of a composite catalyst for nicotinonitrile, it is characterized in that, comprise main active material and auxiliary active agent;
Main active material comprises Cr
2o
3and V
2o
5, or add ammonium molybdate again, the mol ratio of its atom is V: the M in ammonium molybdate
0: Cr=1:0.09 ~ 0.85:0.2 ~ 1.0; Auxiliary active agent is the mixture of following three kinds: the 1. oxide of P or chloride, 2. at least one oxide in Ni, Bi or chloride, be any proportioning when the oxide of Ni, Bi or chloride mixing, 3. at least one oxide in K, Na, Cs or chloride, wherein, be any proportioning when two kinds in K, Na, Cs or three kinds of oxides or chloride mixing; Its atomic ratio is that V:Ni:Bi:P:Na, K are or/and Cs=1:0.0018 ~ 0.81:0.0018 ~ 0.81:0.0018 ~ 0.81:0.003 ~ 0.1.
2. a kind of composite catalyst for the synthesis of nicotinonitrile according to claim 1, is characterized in that, spherical silica gel adopts 50-120 object spherical silica gel.
3. a kind of composite catalyst for the synthesis of nicotinonitrile according to claim 1, is characterized in that, main active material the best is Cr
2o
3and V
2o
5, Cr
2o
31.20 ~ 1.22 grams, V
2o
53.38 gram; Auxiliary active agent the best is P
2o
5, BiCl
3, NiCl
26H
2one in O and KCl, NaCl, CsCl, P
2o
51.10 ~ 1.25 grams, BiCl
30.40 ~ 0.43 gram, NiCl
26H
2o2.40 ~ 2.62 gram, KCl or NaCl or CsCl0.19 ~ 0.22 gram.
4. the preparation method of a kind of composite catalyst for the synthesis of nicotinonitrile as claimed in claim 1, is characterized in that, comprise the steps:
1) press, main active material comprises Cr
2o
3and V
2o
5, or add ammonium molybdate again, the mol ratio of its atom is V: the M in ammonium molybdate
0: Cr=1:0.09 ~ 0.85:0.2 ~ 1.0; Auxiliary active agent is the mixture of following three kinds: the 1. oxide of P or chloride, 2. at least one oxide in Ni, Bi or chloride, be any proportioning when the oxide of Ni, Bi or chloride mixing, 3. at least one oxide in K, Na, Cs or chloride, wherein, be any proportioning when two kinds in K, Na, Cs or three kinds of oxides or chloride mixing; Its atomic ratio is that V:Ni:Bi:P:Na, K are or/and Cs=1:0.0018 ~ 0.81:0.0018 ~ 0.81:0.0018 ~ 0.81:0.003 ~ 0.1; Choose the raw material of main active material and auxiliary active agent;
2) main active material and auxiliary active agent are dissolved, obtain mixed solution; Adopt r-Al
2o
3or spherical silica gel makes carrier, then carrier is poured in above-mentioned mixed solution, make it just to be submerged, stir, activate 6 hours at 773K, namely obtain the composite catalyst for the synthesis of nicotinonitrile.
5. the preparation method of a kind of composite catalyst for the synthesis of nicotinonitrile according to claim 4, is characterized in that, comprise the steps:
1) press, main active material the best is Cr
2o
3, V
2o
5and ammonium molybdate, Cr
2o
31.20 ~ 1.22 grams, V
2o
53.38 grams, ammonium molybdate 0.90 gram ~ 1.06 grams; Auxiliary active agent the best is P
2o
5, BiCl
3, NiCl
26H
2one in O and KCl, NaCl, CsCl, P
2o
51.10 ~ 1.25 grams, BiCl
30.40 ~ 0.43 gram, NiCl
26H
2o2.40 ~ 2.62 gram, KCl or NaCl or CsCl0.19 ~ 0.22 gram; Choose raw material;
2) by V
2o
5and Cr
2o
3join together in 220 ml distilled waters containing 17 grams of oxalic acid, in 353K heating for dissolving, make solution A; P is added again in this solution A
2o
5, BiCl
3, ammonium molybdate, NiCl
26H
2one in O and KCl, NaCl, CsCl, stirs, makes active substance solution B; By r-Al
2o
3or spherical silica gel 95 grams joins in solution B, make it just to be submerged, stir, after 378K is dried, then activate 6 hours under 773K, obtain the composite catalyst for the synthesis of nicotinonitrile.
6. the application of a kind of composite catalyst for the synthesis of nicotinonitrile as described in claim 1 or 4, this composite catalyst is applied to gas phase ammonoxidation method synthesis nicotinonitrile, it is characterized in that, comprises the steps:
1) add the composite catalyst for the synthesis of nicotinonitrile in the reactor, be warming up to 613K ~ 703K; Composite catalyst is 80 grams, and 3-picoline adopts continuous feed, and charging is by 6 Grams Per Hours;
2) by 3-picoline: ammonia: oxygen: 3-picoline, ammonia, air and water vapour, than being=1:1.2 ~ 5:7 ~ 14:1 ~ 15, being sent in reactor, obtained nicotinonitrile by the amount of substance of water vapour.
7. the preparation method of a kind of composite catalyst for the synthesis of nicotinonitrile according to claim 4, is characterized in that, step 2) in, after stirring, then through ageing, oven dry.
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