CN1106314A - Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use - Google Patents
Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use Download PDFInfo
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- CN1106314A CN1106314A CN 94106416 CN94106416A CN1106314A CN 1106314 A CN1106314 A CN 1106314A CN 94106416 CN94106416 CN 94106416 CN 94106416 A CN94106416 A CN 94106416A CN 1106314 A CN1106314 A CN 1106314A
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- China
- Prior art keywords
- catalyst
- oxide
- cyanopyridine
- purposes
- pyridine
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000011149 active material Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl pyridine Chemical compound 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 14
- ITQTTZVARXURQS-UHFFFAOYSA-N beta-methylpyridine Natural products CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 11
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000003426 co-catalyst Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 235000012222 talc Nutrition 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229930194542 Keto Natural products 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 2
- 229910052779 Neodymium Inorganic materials 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052777 Praseodymium Inorganic materials 0.000 claims 1
- 239000006004 Quartz sand Substances 0.000 claims 1
- 229910052772 Samarium Inorganic materials 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 1
- 239000011949 solid catalyst Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 229910052787 antimony Inorganic materials 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229960003350 isoniazid Drugs 0.000 description 2
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 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
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 229960003512 nicotinic acid Drugs 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- COHDGTRFTKHYSJ-UHFFFAOYSA-N 2-Ethyl-5-methylpyridine Chemical compound CCC1=CC=C(C)C=N1 COHDGTRFTKHYSJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940072185 drug for treatment of tuberculosis Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229960005206 pyrazinamide Drugs 0.000 description 1
- IPEHBUMCGVEMRF-UHFFFAOYSA-N pyrazinecarboxamide Chemical compound NC(=O)C1=CN=CC=N1 IPEHBUMCGVEMRF-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing cyanopyridine and a preparation method of the cyanopyridine. The catalyst uses V, Ti and Sb oxide as main active material, at least one oxide of P, Sn, B, Ag, Zr, rare earth element and mixed rare earth element as cocatalyst, and optionally at least one oxide of alkali metal as stabilizer.
Description
The present invention relates to a kind of is raw material with the alkyl pyridine, prepares the catalyst of corresponding cyanopyridine through gas phase ammonoxidation.In particular, what the present invention relates to is raw material with 3-or 4-picoline, prepares the catalyst of corresponding cyanopyridine in molecular oxygen and water vapour atmosphere through gas phase ammonoxidation.
The 3-cyanopyridine is the intermediate of preparation nicotinic acid, niacinamide, and the 4-cyanopyridine is an intermediate of making isonicotinic acid, Pyrazinamide, isoniazid.Nicotinic acid, niacinamide are a kind of of Cobastab, are extensive use of in industries such as medicine, food and feed addictive.The isoniazid is an anti-tuberculosis drugs.
The preparation method of cyanopyridine is known, referring to U.S.4, and 284,781,4,447,612,4,963,687 and 5,028,713; JP74-34673(speciallys permit bulletin) and JP82-156038.
Lummus company is at U.S.4, discloses fusion vanadic anhydride carried catalyst in 284, No. 781, and cigarette nitrile selectivity is 89.7%, and conversion per pass is 51%, and this catalyst selectivity is poor, and conversion ratio is low and need circular regeneration.Degussa company is at U.S.4, and the oxide of having described with Sb and V in 447, No. 612 is the catalyst of main active material, and this catalyst activity content of material is up to 48%, and complicated process of preparation and ammonia consumption are big, and the alkyl pyridine conversion ratio is low.It is carrier that Japan catalyst chemical industrial company has proposed with carborundum in JP74-34673 number, V-Ti is main active material, with P, Nb, K, Cs, Tl, Zn, Gd is the catalyst of co-catalyst, and the sintered silicon carbon that this catalyst employing purity is 98-99% is a carrier, the cost height.The yield of cigarette nitrile and different cigarette nitrile is not high, and has a small amount of unreacted alkyl pyridine in the reacting gas, influences aftertreatment technology.Mitsubishi gas chemical company is at U.S.4, and disclosing a kind of oxide with V, Cr and B in 963, No. 687 is main active material, and the oxide of P and/or Mo is the SiO of co-catalyst
2Carried catalyst, this catalyst activity, selectivity is all not high.Standard Oil Company is at U.S.5, and disclosing with P, V and Mo metal oxide in 028, No. 713 is main active material, and Sb, Fe, W, Cu, K, Cs, B, Sn, Zr, Mn, Nb, U, Bi and Cr are the SiO of co-catalyst
2Carried catalyst.This activity of such catalysts is low, and the alkyl pyridine conversion ratio is not high.Up to the present, do not have a kind of catalyst of prior art to have the conversion ratio height, selectivity is good, the premium properties that the life-span is long.
Therefore, the purpose of this invention is to provide a kind of from the method for alkyl pyridine with high conversion and the corresponding cyanopyridine of highly-selective preparation.
Another object of the present invention provides a kind of catalyst of novelty, and it is in the use of the inventive method, and selectivity is good, the conversion ratio height, and the life-span is long.
A further object of the present invention is that the preparation method of preparation new catalyst used in the present invention is provided.
Other purpose of the present invention, the feature and advantage of others, the specification and the claim gathering of calligraphers are clearer reading.
The invention provides a kind of method for preparing cyanopyridine, it is to make corresponding alkyl pyridine, reacts in the presence of catalyst with the gas and the water vapour of ammonia, molecule-containing keto.This catalyst is with V
2O
5, TiO
2And Sb
2O
3Be main active material, at least a oxide of P, Sn, B, Ag, Zr, rare earth element and lucium is a co-catalyst, selectively adds alkali-metal at least a oxide as stabilizing agent, and it is stated from the heat-resisting inert carrier.
New catalyst of the present invention, main active material are V
2O
5, TiO
2And Sb
2O
3, its gram atom ratio is: at least a oxide of V: Ti: Sb=1: 3-56: 0.1-1.0, P, Sn, B, Ag, Zr and rare earth element and lucium is a co-catalyst, its gram atom ratio to V is 0.001-0.3:1.Preferred Ag, Sn, La and Ce, more preferably mixed rare-earth oxide.
In above-mentioned composition, selectively add alkali-metal at least a oxide, further improve selection of catalysts and heat endurance.The preferred Li of alkali metal, Na, K, Rb, Cs, more preferably K, Rb, to the gram atom of V than being 0.001-0.1.Catalyst activity content of material 1-30%(wt), preferred 5-20%(wt), catalyst of the present invention does not in use need regeneration, and the life-span reaches 3 years.
The raw material for preparing catalyst activity material of the present invention can be used oxide, chloride, inorganic salts such as nitrate, carbonate, phosphate, sulfate, ammonium salt etc.; Organic salt such as oxalates, acetate and amine salt etc. and oxide, hydroxide.Those skilled in the art can determine arbitrarily.
Employed TiO
2Can be commercially available TiO
2, also can be in order to TiCl
4Be the highly active TiO of raw material with the known method preparation
2Perhaps their composition.TiO
2Be anatase titanium dioxide, specific surface is 3-100m
2/ g is preferably 5-50m
2/ g, particle diameter are preferably 0.01-0.3 μ less than 1 μ.
The employed carrier of catalyst of the present invention is the heat-resisting solid material of inertia, as talcum (britesorb), aloxite (AI, carborundum, quartz and pottery etc., preferably talc and carborundum.Carrier can be sphere, cylindrical, annular, preferred spherical.The carrier diameter is 3-12mm, preferred 3-8mm.Carrier can be atresia or loose structure, and its porosity is 0-80%, preferred 0-50%.
Catalyst of the present invention can prepare with known method in the present technique field.For example, with the salt and the oxide dissolution of vanadium and various co-catalysts or be suspended in water and organic solvent in, organic solvent such as ethanol, monoethanolamine, formamide, acetamide, diethylamide, urea and ammonium sulfocyanate etc. add TiO
2, the suspension of preparation active material.Carrier is placed the coating pan that rotating and the rotating machinery of other type, suspension is dripped or sprays on the dry carrier, till active material reaches pre-metering.Catalyst was 400-500 ℃ of activation 2-10 hour.
Method of the present invention can use 2-picoline, 3-picoline, 4-picoline, 2-methyl-5-ethylpyridine and 2-ethyl-5-picoline to be raw material.
The ammoxidation of alkyl-pyridine reaction is to carry out in the fixed bed single tube reactor, and tube inner diameter is 21-40mm, long 1-4m, and the catalyst loading amount is the 0.4-1.2 liter, is thermophore with the fused salt that circulates, the bed temperature thermocouple measurement.The process conditions of reaction are:
Air speed 1000-3000hr
-1
Alkyl pyridine concentration 20-80g/NM
3
Alkyl pyridine: ammonia=1: the 1-10(mole ratio)
Alkyl pyridine: water vapour=1: the 1-20(mole ratio)
Reaction temperature: 300 ℃-450 ℃
In material gas mixture, if air is used as oxygen-containing gas, the concentration of alkyl pyridine can be 20-100g/NM
3, preferred 40-70g/NM
3
Employed ammonia amount in material gas mixture surpasses theoretical amount.When using a large amount of ammonia, must reclaim unreacted ammonia, preferred employed ammonia amount is theoretical amount 2-8 times.
The amount of oxygen is at least theoretical 1.5 times in material gas mixture, is preferably 2-30 times of theoretical amount.Usually air is as oxygen-containing gas, and air can be used the inert gas dilution of nitrogen and so on, CO
2Also can be used as diluent gas with water vapour.
Reaction temperature is 300-450 ℃, and when being lower than 300 ℃, the conversion ratio of alkyl pyridine is low, when being higher than 450 ℃, generates CO
2Amount big, the yield of cyanopyridine is low.Preferable reaction temperature is 340 ℃-400 ℃.
This reaction is under atmospheric pressure carried out usually, also can carry out being higher than atmospheric pressure or being lower than under the atmospheric pressure.
From reaction mixture gas, reclaim product and can adopt suitable method, as reaction mixture gas being cooled to the temperature that product is solidified.Or water or The suitable solvent washing reaction product, to reclaim it, these all are known methods.
The present invention utilizes following limiting examples to further specify, and all percentages are percetage by weight.Except as otherwise noted.
Example 1
With 18 gram V
2O
5Add in the 400ml deionized water that contains 45 gram oxalic acid, heating for dissolving is made the oxalic acid vanadyl aqueous solution of avy blue.In this solution, add 17.3 gram Sb
2O
3, 1.34 the gram AgNO
3, 1.4 gram Ce
2(C
2O
4)
39H
2O, 80 gram formamides and specific surface are 10m
2The anatase titanium dioxide TiO of/g
2253 grams stir and make active material suspension.
With diameter is 6mm, and porosity is 5% talcum ball carrier, 1000 grams, adds diameter and is in the coating pan of rotation of 300mm, with the suspension spraying of active material or be added drop-wise on the dry carrier, reaches till 10% up to the catalyst activity content of material.Then under air atmosphere in 460 ℃ of activation 6 hours, the gram atom ratio that the catalyst activity material that makes is formed is:
V∶Ti∶Sb∶Ag∶Ce＝1∶16∶0.6∶0.04∶0.02
At internal diameter is filling 1000ml catalyst in the single tube reactor of the long 3.6m boiler steel of 25mm control, and bed height is 2.2m, is raw material with 3-or 4-picoline, prepared by ammoxidation 3-or 4-cyanopyridine, process conditions and the results are shown in Table 1.
Raw material and product gc analysis, data are to react sampling result (as follows) after 10 days in the table.
Table 1
Air speed: 1500hr
-1
Water: 3-or 4-picoline=10: the 1(mole ratio)
Picoline conversion ratio :～100%*
Comparative example 3
18 gram V
2O
5, 1.34 the gram AgNO
3, 285 gram specific surface～10m
2/ g and anatase titanium dioxide TiO
2, 1000 gram φ 6mm talcum ball carriers, prepare catalyst and carry out the evaluating catalyst test with example 1 method, at air speed 1500hr
-1, 3-picoline concentration 50g/NM
3, 380 ℃ of reaction temperatures, 3-cyanopyridine yield 84.8mol%.
Claims (17)
1, the catalyst of the corresponding cyanopyridine of a kind of ammoxidation of alkyl-pyridine system is with V
2O
5, TiO
2And Sb
2O
3Be main active material, its gram atom is than being V: Ti: Sb=1: 3-56: 0.1-1.0, and co-catalyst is to be selected from least a oxide of P.Sn, B, Ag, Zr, rare earth element and lucium or their combination.Its gram atom ratio to V is 0.001-0.3: 1, be stated from the inorganic carrier, and the content of the activity of such catalysts material that makes is 1-30% (Wt).
2, by the catalyst of claim 1, wherein the activity of such catalysts content of material is 5-20%(wt).
3, by the catalyst of claim 1, wherein rare earth oxide is CeO
2
4, by the catalyst of claim 1, rare earth oxide wherein is La
2O
3, CeO
2And Pr
6O
11
5, by the catalyst of claim 1, the consisting of of mixed rare-earth oxide wherein: La
2O
324-26%, CeO
248-52%, Nd
2O
315-17%, Pr
6O
115-7%, Sm
2O
3, Gd
2O
3, sum＜2%.
6, by the catalyst of one of claim 1-5, wherein catalyst can select to be added to less a kind of alkali metal oxide, and this oxide is 0.001-0.1:1 to the gram atom ratio of V.
7, by the catalyst of claim 6, wherein alkali metal oxide is the oxide of potassium or rubidium or caesium.
8, by the catalyst of claim 1, wherein inorganic carrier is to be selected from a kind of in talcum, carborundum, aloxite (AI, quartz sand and the pottery.
9, by the catalyst of claim 8, wherein inorganic carrier be annular, sphere and cylindrical in a kind of.
10, by the catalyst of claim 8, wherein the particle diameter of inorganic carrier is φ 3-8mm, and porosity is 0-50%.
11, the Preparation of catalysts method of claim 1-10, wherein catalyst is to prepare with spraying process.
12, use the catalyst of claim 1-10, with the alkyl pyridine is raw material, and the corresponding cyanopyridine of gas phase ammonoxidation system is that solid catalyst is contacted with the admixture of gas that contains alkane pyridine, ammonia, water vapour and molecule-containing keto, make alkyl change into cyano group, make cyanopyridine.
13, by the purposes of claim 12, wherein alkyl pyridine is 3-or 4-picoline.
14, by the purposes of claim 12, its reaction is to carry out in fixed bed.
15, by the purposes of claim 12, wherein air speed is 1000-3000hr
-1
16, by the purposes of claim 12, wherein reaction temperature is 300 ℃-450 ℃.
17, by the purposes of claim 12, wherein alkyl pyridine concentration is 20-100g/NM
3
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| CN94106416A CN1044338C (en) | 1994-06-23 | 1994-06-23 | Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use |
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| CN94106416A CN1044338C (en) | 1994-06-23 | 1994-06-23 | Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use |
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| CN1106314A true CN1106314A (en) | 1995-08-09 |
| CN1044338C CN1044338C (en) | 1999-07-28 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055028C (en) * | 1997-01-13 | 2000-08-02 | 武汉大学 | New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process |
| CN103467370A (en) * | 2013-09-12 | 2013-12-25 | 南通天泽化工有限公司 | Synthesis method of cyanopyridine and derivatives thereof |
| CN106111172A (en) * | 2016-06-22 | 2016-11-16 | 徐州恒鼎生物科技有限公司 | Catalyst for preparing 3-cyanopyridine by catalytic ammoxidation and preparation method thereof |
| CN107537537A (en) * | 2017-09-19 | 2018-01-05 | 河南省科学院高新技术研究中心 | A kind of catalyst that 2 cyanopyridines are prepared for ammoxidation reaction |
| CN109647467A (en) * | 2017-10-12 | 2019-04-19 | 中国石油化工股份有限公司 | Catalyst for pseudocumene oxidation |
| CN111097464A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Vanadium catalyst and preparation method thereof |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3107755A1 (en) * | 1981-02-28 | 1982-09-16 | Degussa Ag, 6000 Frankfurt | CATALYSTS FOR THE PRODUCTION OF 3-CYANPYRIDINE |
| JP2615819B2 (en) * | 1988-04-28 | 1997-06-04 | 三菱瓦斯化学株式会社 | Method for producing cyanopyridine |
| US5055599A (en) * | 1989-06-23 | 1991-10-08 | The Standard Oil Company | Process for the hydrogenation of maleic anhydride to tetrahydrofuran and gamma-butyrolactone |
| CN1026321C (en) * | 1991-08-28 | 1994-10-26 | 复旦大学 | Ordinary-pressure gas-phase hydrogenating synthesis of Y-J lactone with cis-anhydride |
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1994
- 1994-06-23 CN CN94106416A patent/CN1044338C/en not_active Expired - Fee Related
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| CN1055028C (en) * | 1997-01-13 | 2000-08-02 | 武汉大学 | New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process |
| CN103467370A (en) * | 2013-09-12 | 2013-12-25 | 南通天泽化工有限公司 | Synthesis method of cyanopyridine and derivatives thereof |
| CN106111172A (en) * | 2016-06-22 | 2016-11-16 | 徐州恒鼎生物科技有限公司 | Catalyst for preparing 3-cyanopyridine by catalytic ammoxidation and preparation method thereof |
| CN106111172B (en) * | 2016-06-22 | 2018-06-15 | 徐州恒鼎生物科技有限公司 | Catalyst for preparing 3-cyanopyridine by catalytic ammoxidation and preparation method thereof |
| CN107537537A (en) * | 2017-09-19 | 2018-01-05 | 河南省科学院高新技术研究中心 | A kind of catalyst that 2 cyanopyridines are prepared for ammoxidation reaction |
| CN107537537B (en) * | 2017-09-19 | 2020-03-06 | 河南省科学院高新技术研究中心 | Catalyst for preparing 2-cyanopyridine by ammoxidation |
| CN109647467A (en) * | 2017-10-12 | 2019-04-19 | 中国石油化工股份有限公司 | Catalyst for pseudocumene oxidation |
| CN109647467B (en) * | 2017-10-12 | 2020-10-16 | 中国石油化工股份有限公司 | Catalyst for oxidation of pseudocumene |
| CN111097464A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Vanadium catalyst and preparation method thereof |
| CN111097464B (en) * | 2018-10-25 | 2023-08-08 | 中国石油化工股份有限公司 | Vanadium catalyst and preparation method thereof |
| CN116078371A (en) * | 2022-12-30 | 2023-05-09 | 南通立洋化学有限公司 | Catalyst for preparing 2-cyanopyridine by catalytic ammoxidation and application thereof |
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