CN1044338C - 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
- Publication number
- CN1044338C CN1044338C CN94106416A CN94106416A CN1044338C CN 1044338 C CN1044338 C CN 1044338C CN 94106416 A CN94106416 A CN 94106416A CN 94106416 A CN94106416 A CN 94106416A CN 1044338 C CN1044338 C CN 1044338C
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- cyanopyridine
- oxide
- picoline
- purposes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical group CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 25
- -1 alkyl pyridine Chemical compound 0.000 claims description 19
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000454 talc Substances 0.000 claims description 8
- 229910052623 talc Inorganic materials 0.000 claims description 8
- 235000012222 talc Nutrition 0.000 claims description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [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
- 239000006004 Quartz sand Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 229930194542 Keto Natural products 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 239000000470 constituent Substances 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 239000008246 gaseous mixture Substances 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
- 229910052787 antimony Inorganic materials 0.000 abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000011149 active material Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 239000013543 active substance Substances 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- 239000010936 titanium Substances 0.000 description 7
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- BMYPOELGNTXHPU-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxastibolan-2-yl) oxalate Chemical class [Sb+3].[Sb+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BMYPOELGNTXHPU-UHFFFAOYSA-H 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 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
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 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
- 229960003512 nicotinic acid Drugs 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 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
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- COHDGTRFTKHYSJ-UHFFFAOYSA-N 2-Ethyl-5-methylpyridine Chemical compound CCC1=CC=C(C)C=N1 COHDGTRFTKHYSJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-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
- 229910000831 Steel Inorganic materials 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical group [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-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
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 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
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VFQXVTODMYMSMJ-UHFFFAOYSA-N isonicotinamide Chemical compound NC(=O)C1=CC=NC=C1 VFQXVTODMYMSMJ-UHFFFAOYSA-N 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 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
- 229910052721 tungsten Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 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, SnB, Ag, Zr, rare earth element and mixed rare earth element as cocatalyst, optionally at least one oxide of alkali metal as stabilizer, and has high activity, good selectivity and long service life.
Description
The present invention relates to a kind of is raw material with the alkyl pyridine, prepares the catalyzer 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 catalyzer 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 Yi Yansuan, Isonicotinamide, vazadrine.Nicotinic acid, niacinamide are a kind of of vitamins B, are extensive use of in industries such as medicine, food and fodder additives.The vazadrine 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 (special permission bulletin) and JP82-156038.
Lummus company is at U.S.4, discloses fusion Vanadium Pentoxide in FLAKES carried catalyst in 284, No. 781, and cigarette nitrile selectivity is 89.7%, and per pass conversion is 51%, and this catalyst selectivity is poor, and transformation efficiency is low and need cyclic regeneration.Degussa company is at U.S.4, and the oxide compound of having described with Sb and V in 447, No. 612 is the catalyzer of main active substance, and this catalyst activity substances content is up to 48%, and complicated process of preparation and ammonia consumption are big, and the alkyl pyridine transformation efficiency is low.Japan touches that coal chemical industry company proposed with silicon carbide in JP74-34673 number be carrier, V-Ti is main active substance, with P, Nb, K, Cs, Ti, Zn, Gd is the catalyzer of promotor, and the sintered silicon carbon that this catalyzer 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 reactant gases, influences aftertreatment technology.Mitsubishi gas chemical company is at U.S, 4,963, and disclosing a kind of oxide compound with V, Cr and B in No. 687 is main active substance, and the oxide compound of P and/or Mo is the SiO of promotor
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 substance, and Sb, Fe, W, Cu, K, Cs, B, Sn, Zr, Mn, Nb, U, Bi and Cr are the SiO of promotor
2Carried catalyst.This activity of such catalysts is low, and the alkyl pyridine transformation efficiency is not high.Up to the present, do not have a kind of catalyzer of prior art to have the transformation efficiency 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 catalyzer of novelty, and it is in the use of the inventive method, and selectivity is good, the transformation efficiency 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 can be clearer at reading specification sheets and claim postscript.
The invention provides a kind of method for preparing cyanopyridine, it is to make corresponding alkyl pyridine, reacts in the presence of catalyzer with the gas and the water vapor of ammonia, molecule-containing keto.This catalyzer is with V
2O
5, TiO
2And Sb
2O
3Be main active substance, at least a oxide compound of P, Sn, B, Ag, Zr, rare earth element and lucium is a promotor, selectively adds alkali-metal at least a oxide compound as stablizer, and it is stated from the heat-stable inert support.
New catalyst of the present invention, main active substance are V
2O
5, TiO
2And Sb
2O
3, its grammeatom ratio is: at least a oxide compound of V: Ti: Sb=1: 3-56: 0.1-1.0, P, Sn, B, Ag, Zr and rare earth element and lucium is a promotor, its grammeatom 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 compound, further improve selectivity of catalyst and thermostability.The preferred Li of basic metal, Na, K, Rb, Cs, more preferably K, Rb, to the grammeatom of V than being 0.001-0.1.The preferred 5-20% (Wt) of catalyst activity substances content 1-30% (Wt), catalyzer 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 compound, muriate, inorganic salt such as nitrate, carbonate, phosphoric acid salt, vitriol, ammonium salt etc.; Organic salt such as oxalate, acetate and amine salt etc. and oxide compound, oxyhydroxide.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 catalyzer of the present invention is the solid material of heat-stable inertia, as talcum (britesorb), fused alumina, silicon carbide, quartz and pottery etc., preferably talc and silicon carbide.Carrier can be sphere, cylindrical, annular, preferred spherical.The carrier diameter is 3-12mm, preferred 3-8mm.Carrier can be atresia or vesicular structure, and its porosity is 0-80%, preferred 0-50%.
Catalyzer 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 promotors or be suspended in water and organic solvent in, organic solvent such as ethanol, thanomin, methane amide, ethanamide, diethylamide, urea and ammonium sulfocyanate etc. add TiO
2, the suspension of preparation active substance.Carrier is placed the coating pan that rotating and the rotating machinery of other type, suspension is dripped or sprays on the exsiccant carrier, till active substance reaches pre-metering.Catalyzer 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 catalyzer loading amount is the 0.4-1.2 liter, is thermophore with the fused salt that circulates, the bed temperature thermocouple measurement.The processing condition of reaction are:
Air speed 1000-3000hr
-1
Alkyl pyridine concentration 20-80g/NM
3
Alkyl pyridine: ammonia=1: 1-10 (mole ratio)
Alkyl pyridine: water vapor=1: 1-20 (mole ratio)
Temperature of reaction: 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 vapor.
Temperature of reaction is 300-450 ℃, and when being lower than 300 ℃, the transformation efficiency 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 normal atmosphere or being lower than under the normal atmosphere.
From reaction mixture gas, reclaim reaction product and can adopt suitable method, as reaction mixture gas being cooled to reaction product solidified temperature.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 percentage ratios are weight percentage.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 methane amides and specific surface are 10m
2The anatase titanium dioxide TiO of/g
2253 grams stir and make active substance 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 substance or be added drop-wise on the exsiccant carrier, reaches till 10% up to the catalyst activity substances content.Then under air atmosphere in 460 ℃ of activation 6 hours, the grammeatom 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 catalyzer 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, and prepared by ammoxidation 3-or 4-cyano group pyrrole are fixed, processing condition 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: 1 (mole ratio)
Picoline transformation efficiency :~100%*
*~100% the expression>99.97% following example in if no special instructions the picoline transformation efficiency be~100%.
3-picoline concentration g/NM 3 | 4-methyl pyrrole is decided concentration g/NM 3 | Temperature of reaction ℃ | Ammonia: 3-or 4-picoline mole ratio | 3-cyanopyridine yield mol% | 4-cyanopyridine yield mol% |
40 60 | / / | 380 380 | 2.5∶1 2.5∶1 | 90.5 90.3 | / / |
/ / | 50 60 | 360 355 | 2∶1 2∶1 | / / | 91.5 92.3 |
Example 2
Remove Ce
2(C
2O
4)
39H
2O is outside 0.7 gram, adds La (NO again
3)
36H
2O 0.68 gram, Praseodymium trioxide (Pr
6O
11) 0.067 gram, other is with example 1, and 3-picoline concentration is 60g/NM
3, 380 ℃ of temperature of reaction, 3-cyanopyridine yield is 90.7mol%.
Example 3
Divided by mixed rare-earth oxide (with A
xO
yExpression, it consists of: 24-26%La
2O
348-52%CeO
25-17%Nd
2O
35-7%Pr
6O
11Sm
2O
3, Gd
2O
3, sum<2%) replaced C e
2(C
2O
4)
39H
2Outside the O, other is with example 1.The rare earth oxide amount is in cerium oxide, so V: A=1: 0.02 (grammeatom ratio), the AxOy add-on is 0.68 gram, 3-picoline concentration is 60g/NM
3, 380 ℃ of temperature of reaction, 3-cyanopyridine yield is 91.1mol%.
Example 4
The catalyst activity material consists of: 18 gram V
2O
5, 45 gram oxalic acid, 11.5 gram Sb
2O
3, 1.34 the gram AgNO
3, 0.51 the gram mixed rare-earth oxide, 0.23 the gram Rb
2CO
3, specific surface is 10m
2The TiO of/g
2285 grams, methane amide 50 grams, ethanol 50 grams, 450 milliliters of deionized waters, this Preparation of catalysts method and reaction unit and processing condition are with example 1, and test-results sees Table 2.
Table 2*
Air speed hr -1 | 3-picoline concentration g/NM 3 | 4-methyl pyrrole is decided concentration g/NM 3 | Temperature of reaction ℃ | 3-cyanopyridine yield mol% | 4-cyanopyridine yield mol% |
1500 1500 1600 1600 | 40 60 / / | / / 50 60 | 385 380 365 360 | 92.1 91.7 / / | / / 92.7 94.1 |
Example 5
Except that Silver Nitrate replaced with primary ammonium phosphate, nitric acid tin, boric acid and zirconium white, other was with example 4, and test-results sees Table 3.
Table 3*
V: promotor grammeatom ratio | Air speed hr -1 | 3-methyl pyrrole is decided concentration g/NM 3 | Temperature of reaction ℃ | 3-cyanopyridine yield mol% |
V∶P=1∶0.08 | 1500 1500 | 40 60 | 385 380 | 91.9 91.5 |
V∶Sn=1∶0.06 | 1500 1500 | 40 60 | 385 380 | 91.0 91.2 |
V∶B=1∶0.04 | 1400 | 40 | 385 | 90.2 |
V∶Zr=1∶0.04 | 1400 | 40 | 385 | 90.5 |
Example 6
Except that not adding the rare-earth oxidation beyond the region of objective existence, other are with example 4, and test-results sees Table 4:
Table 4
3-picoline concentration g/NM 3 | Temperature of reaction ℃ | 3-picoline transformation efficiency % | 3-cyanopyridine yield mol% |
40 | 385 | ~100 | 88.5 |
60 | 385 | 98.6 | 88.9* |
*: calculate with the 3-picoline that has transformed.
Example 7
Remove with 0.77 gram CsNO
3Replace Pb
2CO
3Outward, other is with example 4,3-or 4-picoline concentration 50g/nm
3, 385 ℃, 365 ℃ of temperature of reaction, 3-cyanopyridine yield is that 91.2mol%, 4-cyanopyridine yield are 93.6mol%.
Example 8
With the Sb in the 18.7 gram vanadic acid antimony replacement examples 4
2O
3With 7.2 gram V
2O
5, or with 20.1 gram antimony oxalates replacement Sb
2O
3, experimental result sees Table 5.
Table 5
Contain the antimony material | Day in reaction times | 3-picoline concentration g/NM 3 | Temperature of reaction ℃ | 3-picoline yield mol% |
Antimonous oxide | 5 10 | 50 50 | 390 385 | 88.3 91.7 |
Antimony oxalate | 5 10 | 50 50 | 385 385 | 90.6 91.7 |
Vanadic acid antimony | 5 10 | 50 50 | 385 385 | 91.5 91.8 |
By in the table as can be known, add the inductive phase that vanadic acid antimony or antimony oxalate can reduce catalyzer.
Example 9
285 gram specific surfaces in example 4 are 10M
2The TiO of/g
2, reduce to 158 gram (V: Ti=1: 10) and wherein contain 10% by TiCl
4The active TiO of preparation
2, other are with example 4, and test-results sees Table 6.
Table 6
3-picoline concentration g/NM 3 | 4-picoline concentration g/NM 3 | Temperature of reaction | 3-cyanopyridine yield mol% | 4-cyanopyridine yield mol% |
50 70 / / | / / 50 70 | 375 370 355 350 | 91.4 91.9 / / | / / 91.8 93.1 |
As can be known from Table 6, add active TiO
2, can suitably reduce temperature of reaction, improve the load of catalyzer.
Example 10
Except that adopting talcum ring, silicon carbide ball, alumina balls, quartz sand ball, Ceramic Balls is the carrier, and other are with example 4.Test-results sees Table 7.
Table 7
The kind of carrier transitivity | 3-picoline concentration g/NM 3 | Temperature of reaction ℃ | 3-cyanopyridine yield mol% | |||
Content % | Particle diameter mm | Porosity % | ||||
Talcum cyclohexyl carbodiimide silicon ball alumina balls quartz sand ball porcelain ball | Talcum powder>65 SiC>85 α-Al 2O>85 quartz sands>80 porcelain powder>90 | φ6×6×1.5 φ6 φ5 φ5 φ5 | 5-10 35-40 35-40 20-25 0-10 | 60 60 60 40 40 | 385 380 380 380 380 | 91.8 91.6 91.1 89.1 91.4 |
Fully aware of, those skilled in the art can carry out various modifications or improvement to the present invention by above-mentioned description and discussion, but do not break away from the spirit and scope of foregoing description, or the scope of claims.
Comparative example 1
18 gram V
2O
5, 19.3Sb
2O
3, specific surface~10m
2The anatase titanium dioxide TiO of/g
2285 grams, 1000 gram φ 6mm talcum balls prepare catalyzer, catalyst activity material grammeatom ratio: V: Ti: Sb=1 with the method for example 1: 18: 0.6, with the testing apparatus of example 1.
At air speed 1500hr
-1, 3-picoline concentration 40g/NM
3, 380 ℃ of temperature of reaction, 3-cyanopyridine yield 86.5mol%.
Comparative example 2
18 gram V
2O
5, 1.4 gram Ce
2(C
2O
4)
39H
2O, 285 gram specific surface~10m
2/ g, anatase titanium dioxide TiO
2, 1000 gram φ 6mm silicon carbide balls, prepare catalyzer with example 1 method, catalyst activity material grammeatom ratio: V: Ti: Ce=1: 18: 0.02, test with the experimental installation of example 1, the results are shown in Table 8.
Table 8
Air speed | 3-methyl pyrrole concentration g/NM 3 | 4-picoline concentration g/NM 3 | Temperature of reaction ℃ | 3-cyanopyridine yield mol% | 4-cyanopyridine yield mol% |
1500 1500 1600 1600 | 40 60 / / | / / 50 60 | 375 375 355 355 | 87.2 88.6 / / | / / 90.4 89.7 |
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 catalyzer and carry out the evaluating catalyst test with example 1 method, at air speed 1500hr
-1, 3-picoline concentration 50g/NM
3, 380 ℃ of temperature of reaction, 3-cyanopyridine yield 84.8mol%.
Claims (16)
1. the catalyzer of the corresponding cyanopyridine of ammoxidation of alkyl-pyridine system is with V
2O
5, TiO
2And Sb
2O
3Be main active constituent, its grammeatom is than being V: Ti:Sb=1: 3-56: 0.1-1.0, and promotor is to be selected from least a oxide compound of P, Sn, B, Ag, Zr, rare earth element and lucium or their combination; Its grammeatom ratio to V is 0.001-0.3: 1, be stated from the inorganic carrier, and the content of the activity of such catalysts component that makes is 1-30%, by weight;
Wherein inorganic carrier is to be selected from a kind of in talcum, silicon carbide, fused alumina, quartz sand and the pottery.
2. by the catalyzer of claim 1, wherein activity of such catalysts component content is 5-20%, by weight.
3. by the catalyzer of claim 1, wherein rare earth oxide is CeO
2
4. by the catalyzer of claim 1, rare earth oxide wherein is La
2O
3, CeO
2And Pr
6O
11
5. by the catalyzer 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
3With Gd
2O
3Sum<2%, by weight.
6. by the catalyzer of claim 1, wherein catalyzer adds at least a alkalimetal oxide, and this oxide compound is 0.001-0.1 to the grammeatom ratio of V: 1.
7. by the catalyzer of claim 6, wherein alkalimetal oxide is the oxide compound of potassium or rubidium or caesium.
8. by the catalyzer of claim 1, wherein inorganic carrier be a kind of in annular, sphere and the garden cylindricality.
9. by the catalyzer of claim 1, wherein the particle diameter of inorganic carrier is φ 3-8mm, and porosity is 0-50%.
10. the Preparation of catalysts method of one of claim 1-9, wherein catalyzer is to prepare with spraying method.
11. catalyzer with one of claim 1-9, with the alkyl pyridine is raw material, and the corresponding cyanopyridine of gas phase ammonoxidation system is that solid catalyst is contacted with the gaseous mixture that contains alkane pyridine, ammonia, water vapour and molecule-containing keto, make alkyl change into cyano group, make cyanopyridine.
12. by the purposes of claim 11, wherein alkyl pyridine is 3-picoline or 4-picoline.
13. by the purposes of claim 11, its reaction is to carry out in fixed bed.
14. by the purposes of claim 11, wherein air speed is 1000-3000hr
-1
15. by the purposes of claim 11, wherein temperature of reaction is 300 ℃-450 ℃.
16. by the purposes of claim 11, wherein alkyl pyridine concentration is 20-100g/NM
3
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN94106416A CN1044338C (en) | 1994-06-23 | 1994-06-23 | Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN94106416A CN1044338C (en) | 1994-06-23 | 1994-06-23 | Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1106314A CN1106314A (en) | 1995-08-09 |
CN1044338C true CN1044338C (en) | 1999-07-28 |
Family
ID=5032559
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94106416A Expired - Fee Related CN1044338C (en) | 1994-06-23 | 1994-06-23 | Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1044338C (en) |
Families Citing this family (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 |
CN103467370B (en) * | 2013-09-12 | 2015-07-22 | 南通天泽化工有限公司 | Synthesis method of cyanopyridine and derivatives 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 |
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 |
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 |
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 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4447612A (en) * | 1981-02-28 | 1984-05-08 | Degussa Aktiengesellschaft | Catalysts for the production of 3-cyanopyridine |
US4963687A (en) * | 1988-04-28 | 1990-10-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing cyanopyridines |
CN1048172A (en) * | 1989-06-23 | 1991-01-02 | 标准石油公司 | Maleic anhydride hydrogenation changes into tetrahydrofuran (THF) and the used coated catalysts of gamma-butyrolactone |
CN1058400A (en) * | 1991-08-28 | 1992-02-05 | 复旦大学 | Ordinary-pressure gas-phase hydrogenating synthesis of y-j lactone with cis-anhydride |
-
1994
- 1994-06-23 CN CN94106416A patent/CN1044338C/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4447612A (en) * | 1981-02-28 | 1984-05-08 | Degussa Aktiengesellschaft | Catalysts for the production of 3-cyanopyridine |
US4963687A (en) * | 1988-04-28 | 1990-10-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing cyanopyridines |
CN1048172A (en) * | 1989-06-23 | 1991-01-02 | 标准石油公司 | Maleic anhydride hydrogenation changes into tetrahydrofuran (THF) and the used coated catalysts of gamma-butyrolactone |
CN1071421A (en) * | 1989-06-23 | 1993-04-28 | 标准石油公司 | The catalysis process for preparing tetrahydrofuran (THF) and gamma-butyrolactone by maleic anhydride |
CN1058400A (en) * | 1991-08-28 | 1992-02-05 | 复旦大学 | Ordinary-pressure gas-phase hydrogenating synthesis of y-j lactone with cis-anhydride |
Also Published As
Publication number | Publication date |
---|---|
CN1106314A (en) | 1995-08-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1232504C (en) | Process for producing acrylonitrile, catalyst used therein and process for producing the same | |
US3926846A (en) | Catalysts for the preparation of phthalic anhydride | |
JP4521019B2 (en) | Process for the production of aromatic or heteroaromatic nitriles and supported catalysts for the process | |
CN1084643C (en) | Catalysts for preparing chlorine from mydrogen chloride | |
US20040106817A1 (en) | Catalyst for the manufacture of acrylonitrile | |
CN1116110C (en) | Regeneration method of molybdenum-containing oxide fluidized bed catalyst | |
JP4097749B2 (en) | Catalytic oxidation catalyst | |
CN1044338C (en) | Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use | |
CN1164570C (en) | Process for producing acrylonitrile, catalyst used therein and process for producing the same | |
JP3939373B2 (en) | Supported catalysts suitable for ammonooxidation | |
CN101797510B (en) | Catalyst containing rare earth for ammoxidation of alkane | |
CZ284488B6 (en) | Process of regenerating catalysts based on metal oxides | |
CN1047959C (en) | Supported catalyst for preparing phthalic anhydride | |
JPS62120351A (en) | Manufacture of aromatic nitrile | |
US3870655A (en) | Catalyst for the preparation of anthraquinone | |
CN113877569B (en) | Catalyst for producing pyromellitic dianhydride and preparation method thereof | |
US6153767A (en) | Production process for pyromellitic dianhydride | |
CN101993362B (en) | Method for producing oxalic ester through coupling CO | |
CN1151135C (en) | Catalyst for preparing 3-cyanopyridine and preparation and use thereof | |
US4541964A (en) | Production of methacrylonitrile | |
KR870000919B1 (en) | Method for manufacture of phthalic anhydride | |
EP1617946B1 (en) | Ti-pillared clay based vanadia catalyst and process for preparation | |
US6344568B1 (en) | Catalyst for gas phase partial oxidation | |
CN1055285C (en) | Catalyst for propylene and isobutylene ammoxidation fluidized bed | |
CN111097464B (en) | Vanadium catalyst and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 19990728 Termination date: 20100623 |