CN103721722A - Composite oxide catalyst and preparation method thereof - Google Patents
Composite oxide catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN103721722A CN103721722A CN201210382522.3A CN201210382522A CN103721722A CN 103721722 A CN103721722 A CN 103721722A CN 201210382522 A CN201210382522 A CN 201210382522A CN 103721722 A CN103721722 A CN 103721722A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hours
- gas
- roasting
- molecular oxygen
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims description 16
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 66
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 64
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 64
- 239000012298 atmosphere Substances 0.000 claims abstract description 47
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 28
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 7
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 241000219793 Trifolium Species 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 24
- 239000001301 oxygen Substances 0.000 abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 abstract description 24
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 50
- 239000000243 solution Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 229910002090 carbon oxide Inorganic materials 0.000 description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 22
- 230000001590 oxidative effect Effects 0.000 description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 9
- 229940010552 ammonium molybdate Drugs 0.000 description 9
- 235000018660 ammonium molybdate Nutrition 0.000 description 9
- 239000011609 ammonium molybdate Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 239000004323 potassium nitrate Substances 0.000 description 8
- 235000010333 potassium nitrate Nutrition 0.000 description 8
- 239000011863 silicon-based powder Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 4
- QGWDKKHSDXWPET-UHFFFAOYSA-E pentabismuth;oxygen(2-);nonahydroxide;tetranitrate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QGWDKKHSDXWPET-UHFFFAOYSA-E 0.000 description 4
- 230000008092 positive effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011551 heat transfer agent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- -1 uniformly mixing Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst and preparation method thereof: Mo12BibFecCodXeYfZgOi, wherein, X is selected from W, Sb, As, P, Ni, Sn, Ce and Pb; Y is selected from Zn, Cr, Mn, Ru, Ag, Pd and La; Z is selected from Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba; b is 0.1-7; c is 0.5-8; d is 1-6; e is 0.1-3; f is 0-1; g is 0-2; h is determined by oxidation state of each element. The preparation method comprises the following steps: (i) providing a precursor, mixing, pre-roasting, moulding, and obtaining a preformed catalyst; (ii) roasting the preformed catalyst in gas which contains at least 5-40% of one from ammonia gas, hydrogen, propylene and acrolein, and 0-19% of oxygen and the balance of inert gas at 380-520 DEG C for 3-20 hours; (iii) roasting gas in the atmosphere containing 21-35% of molecular oxygen at 450-540 DEG C for 3-20 hours, and the volume space velocity of roasting gas to catalyst is 50-2000h<-1>.
Description
Technical Field
The invention relates to a composite oxide catalyst, which can be used for preparing unsaturated aldehyde and unsaturated acid with high activity and high selectivity, can effectively inhibit the generation of carbon monoxide and carbon dioxide, has high catalyst life and high catalyst stability, and is suitable for tail gas circulation or non-tail gas circulation processes. The invention also relates to a preparation method of the composite oxide catalyst.
Background
Unsaturated acids such as acrylic acid and methacrylic acid are important organic chemical products, and are industrially prepared mainly by a two-step oxidation method of olefin. In order to increase the capacity of the production plant, industrial processes generally employ a method of increasing the propylene concentration in the feed gas or a method of increasing the space velocity of propylene or expanding the capacity of the reactor, both of which are undoubtedly more economical and convenient methods.
The conventional olefin oxidation catalyst is usually a Mo-Bi-O-based composite oxide. Since the oxidation reaction of olefin is accompanied by a large amount of heat generation, a high temperature portion or hot spot portion is formed in the catalyst bed, and such heat accumulation at the hot spot portion of local high temperature causes deterioration of the catalyst performance, resulting in accelerated deactivation of the catalyst.
To solve the problem of hot spot accumulation at such local high temperature, many effective technical means are proposed in the prior art, for example, JP 113730/80, CN 1162382C, CN 1599708a, JP3294239 and the like propose technical means for solving the problem of hot spot accumulation at such local high temperature, which mainly include the following methods:
(i) diluting the catalyst bed with an inert material;
(ii) gradually filling a catalyst with particles from large to small along the change of the bed layer position from the raw material inlet to the raw material outlet of the reactor;
(iii) gradually filling a catalyst with the active component ratio from low to high along the change of the bed layer position from the raw material inlet to the raw material outlet of the reactor;
(iv) gradually filling a catalyst with the activity from low to high along the change of the bed layer position from the raw material inlet to the raw material outlet of the reactor; and/or
(v) The raw gas inlet of the reactor is charged with a catalyst for reducing the initial activity by a toxic substance.
Although these methods described above provide some improvement in suppressing the temperature of the hot spot, when the above methods are employed, the amount of the catalyst active material at the feed gas inlet of the reactor is smaller than that at the outlet, or the activity of the catalyst at the inlet is lower than that at the outlet, with the result that the catalyst at the inlet is deactivated faster than that at the outlet, affecting the stability of the catalyst in operation under high yield conditions for a long period of time.
In addition, the use of toxic substances leads to the stability of the catalyst being influenced after a longer oxidation reaction after adsorption of the toxic components on the active sites of the catalyst. In general, the above measures only make adjustments to the packing scheme during the use of the catalyst, and do not substantially improve the catalyst itself.
The prior art also mentions improvements in catalyst performance, for example US 4,217,309, US 4,250,339, US 4,258,217, US 4,267,385, CN 100354042C, CN 1255366C, US 5,981,804, CN1168696C, US 5,808,142, CN 1042200C, etc. all relate to improved catalysts, including the addition of trace elements and the relative amounts between elements, changing the carrier of the catalyst and the acidity and basicity of the carrier, changing part of the raw materials of the catalyst, changing reaction conditions such as operation at higher temperatures, etc., thereby affecting and changing the performance of the catalyst. However, the catalysts mentioned in the above documents do not achieve good effect, and the introduction of excessive elements and components increases the complexity of the preparation procedure and preparation process of the catalyst, and is more likely to cause the problem of non-uniformity of components, and the use at higher temperature may affect the selectivity of the catalyst or reduce the service life of the catalyst.
In addition, another serious problem caused by local high-temperature heat accumulation at the hot spot is that excessive oxidation reaction occurs, so that a large amount of carbon oxide, which is a deep oxidation product, is generated, and the selectivity and yield of the main product are reduced. The formation of a large amount of carbon oxide will in turn lead to the generation of more heat, further deteriorating the selectivity of the catalyst.
Accordingly, there remains a need in the art to provide a catalyst having improved selectivity and low carbon oxide formation which not only has a positive effect on increasing the yield of the desired product, but also has a positive effect on reducing the heat accumulation at hot spots.
There is also a need in the art to provide methods for preparing such catalysts.
Disclosure of Invention
It is therefore an object of the present invention to provide a catalyst having improved selectivity and low carbon oxide formation, which not only has a positive effect on increasing the yield of the desired product, but also has a positive effect on reducing the heat accumulation at hot spots.
It is another object of the present invention to provide a method for preparing the catalyst.
Accordingly, one aspect of the present invention relates to a catalyst having the general formula:
Mo12BibFecCodXeYfZgOi，
wherein,
x is at least one element selected from the group consisting of W, Sb, As, P, Ni, Sn, Ce and Pb;
y is at least one element selected from Zn, Cr, Mn, Ru, Ag, Pd and La;
z is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr, and Ba;
b is 0.1 to 7;
c is 0.5 to 8;
d is 1 to 6;
e is 0.1 to 3;
f is 0 to 1;
g is 0-2;
h is a number determined by the oxidation state of each of the above elements;
the method is characterized in that the catalyst is prepared by the following method:
(i) providing precursors of the elements, and obtaining a formed catalyst by mixing, pre-roasting, coating on an inert carrier or directly forming;
(ii) roasting the obtained molded catalyst for 3-20 hours at 380-520 ℃ in an atmosphere containing at least 5-40% of ammonia gas, hydrogen gas, propylene, acrolein, 0-19% of molecular oxygen and the balance of inert gas; and
(iii) roasting for 3-20 hours at 450-540 ℃ in an atmosphere containing 21-50% of molecular oxygen, wherein the volume space velocity of roasting gas relative to the catalyst is 50-2000 h-1Thus obtaining the catalyst.
In another aspect, the present invention relates to a method for preparing a composite metal oxide catalyst of the formula:
Mo12BibFecCodXeYfZgOi，
wherein,
x is at least one element selected from the group consisting of W, Sb, As, P, Ni, Sn, Ce and Pb;
y is at least one element selected from Zn, Cr, Mn, Ag, Pd, La and Ru;
z is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr, and Ba;
b is 0.1 to 7;
c is 0.5 to 8;
d is 1 to 6;
e is 0.1 to 3;
f is 0 to 1;
g is 0 to 2;
h is a number determined by the oxidation state of each element described above.
It comprises the following steps:
(i) providing precursors of the elements, and obtaining a formed catalyst by mixing, pre-roasting, coating on an inert carrier or directly forming;
(ii) roasting the obtained molded catalyst for 3-20 hours at 380-520 ℃ in an atmosphere containing at least 5-40% of ammonia gas, hydrogen gas, propylene, acrolein and 0-19% of molecular oxygen and the balance of inert gas; and
(iii) roasting for 3-20 hours at 450-540 ℃ in an atmosphere containing 21-50% of molecular oxygen, wherein the volume space velocity of roasting gas relative to the catalyst is 50-2000 h-1Thus obtaining the catalyst.
Detailed Description
The invention relates to a composite oxide catalyst, which has the general formula:
Mo12BibFecCodXeYfZgOi，
wherein Mo represents molybdenum, Bi represents bismuth, Fe represents iron, and Co represents cobalt;
x is at least one element selected from the group consisting of W, Sb, As, P, Ni, Sn, Ce and Pb; preferably at least one element selected from the group consisting of W, Ce, Sb, As, P and Ni; more preferably at least one element selected from W, Ce and Ni;
y is at least one element selected from the group consisting of Zn, Cr, Mn, Ru, Ag, Pd and La, preferably at least one element selected from the group consisting of La, Cr and Ru;
z is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba; preferably at least one element selected from the group consisting of Na, K, Li, Rb and Cs; more preferably at least one element selected from the group consisting of Na and K;
b is 0.1 to 7, preferably 1 to 6, more preferably 2 to 5; or a range of values formed from 0.1, 7, 1, 6, 2, 5 as any of the endpoints;
c is 0.5 to 8, preferably 1 to 6, more preferably 2 to 5; or a range of values formed from 0.5, 8,1, 6, 2, 5 as any of the endpoints;
d is 1 to 6, preferably 2 to 5, more preferably 3 to 4; or a range of values formed by any endpoints of 1, 6, 2, 5, 3, 4;
e is 0.1 to 3, preferably 0.5 to 2.5, more preferably 0.8 to 2; or a range of values formed by any of endpoints 0.1, 3, 0.5, 2.5, 0.8, 2;
f is 0 to 1, preferably 0.2 to 0.8, more preferably 0.4 to 0.6; or a range of values formed by any of endpoints 0, 1, 0.2, 0.8, 0.4, 0.6;
g is 0 to 2, preferably 0.2 to 1.8, more preferably 0.5 to 1.5; or a range of values formed by any of endpoints 0, 2, 0.2, 1.8, 0.5, 1.5;
h is a number determined by the oxidation state of each element described above.
The above-mentioned composite oxide catalyst of the present invention is prepared by a special process of the present invention, which comprises the steps of:
(i) providing precursors of the elements, and obtaining the formed catalyst by mixing, pre-roasting, coating on an inert carrier or directly forming.
The above-mentioned step of obtaining a shaped catalyst of the present invention is not particularly limited per se, and may be a step which is conventional in the art. In one embodiment of the present invention, the step of forming the shaped catalyst of the present invention comprises: dissolving precursors of each element in a solvent, uniformly mixing, drying, pre-roasting, optionally adding a diluted heat-conducting agent, a preformed binder and a lubricant, uniformly mixing, and forming into a formed catalyst with a required shape.
In another embodiment of the present invention, the step of forming the shaped catalyst of the present invention comprises: precursors of each element are dissolved in a solvent and mixed uniformly, pre-roasted after drying, then a dilute heat-conducting agent, a preformed binder and a lubricant are optionally added and mixed uniformly to form slurry, and then the slurry is coated on a catalyst carrier with a required shape.
The solvent suitable for the mixing of the present invention is not particularly limited, and may be any conventional solvent known in the art, for example, polar solvents such as water, alcohol, etc. For cost and environmental reasons, it is preferred to use water as solvent for the process of the invention.
Suitable precursors are not particularly limited and may be any suitable precursor known in the art. In a preferred embodiment of the invention, water-soluble precursors are used, for example nitrates of the above-mentioned elements.
The drying temperature and drying time suitable for the method of the present invention are not particularly limited and may be any conventional drying temperature and drying time known in the art. In a preferred embodiment of the invention, water is used as solvent and the drying temperature is 100-160 ℃, preferably 130-150 ℃. The drying time is 10 minutes to 24 hours, preferably 30 minutes to 10 hours, more preferably 1 to 5 hours.
The pre-firing temperature and the pre-firing time suitable for the method of the present invention are not particularly limited and may be any conventional pre-firing temperature and pre-firing time known in the art. In a preferred embodiment of the present invention, the pre-baking temperature is 160-; the pre-baking time is 30 minutes to 24 hours, preferably 2 hours to 15 hours, more preferably 4 hours to 10 hours.
The dilute heat transfer agent suitable for use in the process of the present invention is not particularly limited and may be any suitable dilute heat transfer agent known in the art, for example, silica fume, silicon carbide, alumina, silicon.
The binder suitable for the method of the present invention is not particularly limited and may be any conventional binder known in the art, for example, it may be selected from polyethylene glycol, polyvinyl alcohol, polyacrylamide, silica sol, ammonium nitrate, ceramic fiber.
The lubricant suitable for use in the process of the present invention is not particularly limited and may be any conventional lubricant known in the art, for example, it may be selected from water, graphite, sesbania powder, talc.
The shape of the shaped catalyst of the present invention is not particularly limited, depending on the requirements of a particular catalytic reaction. For example, the shaped catalyst may have a solid or hollow shape such as a sphere, a cylinder, a clover, a gear, and the like. As described above, the shaped catalyst of the present invention may be obtained by shaping the composite catalyst itself into the above-described shape, or may be obtained by coating the composite oxide catalyst of the present invention on a catalyst support having the above-described shape.
The "catalyst carrier having the above-mentioned shape" to be applicable is not particularly limited, and may be any conventional catalyst carrier known in the art. Non-limiting examples of suitable catalyst supports are, for example, aluminum dihydrogen phosphate catalyst supports, silicon carbide catalyst supports, graphite catalyst supports, silicon powder catalyst supports, alumina catalyst supports or mixed supports of two or more of the above catalyst supports.
In a preferred embodiment of the present invention, the step (i) of preparing a shaped catalyst comprises the steps of:
(a) dissolving molybdate (such as ammonium molybdate) and nitrate precursor X, Y or Z in water to obtain solution (1);
(b) dissolving nitrate precursors of Fe, Co and Ni in water, adding nitrate precursors of nitric acid and Bi, and then adding X, Y or Z nitrate precursors to obtain a solution (2);
(c) mixing the solutions (1) and (2) to obtain slurry, and drying the slurry at the temperature of 100-160 ℃;
(d) pre-roasting the obtained dry product at the temperature of 160-280 ℃ for 30 minutes to 24 hours;
(e) adding 0-50% of diluent heat-conducting agent, 0.01-10% of binder and 0.01-8% of lubricant into the pre-roasted product, uniformly mixing, and coating on solid or hollow inert carriers such as spherical, cylindrical, clover-shaped, gear-shaped and the like, or directly forming into the specific shape to obtain the formed catalyst.
(ii) The obtained shaped catalyst is calcined at 380-520 ℃ for 3-20 hours in the range of inert gas or in the atmosphere containing at least one of 5-40% (v/v) ammonia gas, hydrogen gas, propylene, acrolein, 0-19% (v/v) molecular oxygen and the balance of inert gas.
The process of the invention comprises the step of calcining the shaped catalyst in a low oxidizing atmosphere having a molecular oxygen content equal to or less than 19% by volume, preferably equal to or less than 16% by volume, more preferably equal to or less than 10% by volume, preferably equal to or less than 5% by volume, preferably equal to or less than 3% by volume. For example, the low oxidizing atmosphere may be any content range including 0 vol%, 19 vol%, 16 vol%, 10 vol%, 5 vol%, and 3 vol%.
In addition to the molecular oxygen content, the balance of the gas in the low oxidizing atmosphere is selected from the group consisting of inert gases, hydrogen, propylene, acrolein, ammonia, or mixtures of two or more thereof, wherein the amount of ammonia does not exceed 40% by volume of the total, for example 5% to 40% (v/v).
In a preferred embodiment of the present invention, the atmosphere for calcining the shaped catalyst prepared by the above method comprises 0 to 19% by volume of molecular oxygen, 5 to 40% by volume of ammonia gas and the balance of nitrogen gas. In another preferred embodiment of the present invention, the atmosphere for calcining the shaped catalyst prepared by the above method comprises 0 to 19% by volume of molecular oxygen and the balance of nitrogen gas. In still another preferred embodiment of the present invention, the atmosphere for calcining the shaped catalyst obtained by the above method comprises acrolein, 0 to 19% by volume of molecular oxygen and nitrogen.
The calcination temperature of the formed catalyst of the present invention is 380-520 ℃, preferably 480 ℃ at 400-.
The calcination time of the shaped catalyst of the present invention is 1 to 48 hours, preferably 3 to 24 hours, and more preferably 5 to 16 hours. For example, the first-calcined molded catalyst is obtained from the calcination time defined by any two of 1 hour, 48 hours, 3 hours, 24 hours, 5 hours, and 16 hours as endpoints.
(iii) Roasting for 3-20 hours at 450-540 ℃ in an atmosphere containing 21-50% of molecular oxygen, wherein the volume space velocity of roasting gas relative to the catalyst is 50-2000 h-1Thus obtaining the catalyst.
The method of the invention also comprises the step of carrying out secondary roasting on the formed catalyst after the primary roasting. The second calcination in the process of the present invention is carried out in an atmosphere containing 21% by volume or more of molecular oxygen, preferably 21 to 50% by volume, more preferably 21 to 45% of molecular oxygen and the balance of inert gas, preferably 21 to 40% of molecular oxygen and the balance of inert gas, more preferably 21 to 35% of molecular oxygen and the balance of inert gas.
For example, the second firing is performed in an atmosphere containing 21% by volume or more of molecular oxygen (balance being inert gas), in an atmosphere containing 35% by volume or more of molecular oxygen (balance being inert gas), or in an atmosphere containing 50% by volume or more of molecular oxygen (balance being inert gas).
The inert gas to be used is not particularly limited, and may be an inert gas conventional in the art, such as nitrogen, helium, argon, or a mixed gas of two or more thereof.
In one example of the present invention, the second firing is performed in an atmosphere of a molecular oxygen content range formed by taking 21 vol%, 50 vol%, 45 vol%, 40 vol%, 35 vol% as an end point and a balance of an inert gas.
The second roasting in the method of the invention is carried out at a temperature of 450-540 ℃, preferably at a temperature of 450-520 ℃, more preferably at a temperature of 460-510 ℃ for 3-20 hours, preferably for 5-18 hours, more preferably for 6-15 hours. The volume space velocity of the roasting gas relative to the catalyst is 50-2000 h-1Preferably 100--1More preferably 300--1Thus obtaining the catalyst.
The catalyst obtained by the method of the invention can be used for the reaction of preparing acrolein and acrylic acid by partial oxidation of propylene or the reaction of preparing methacrolein and methacrylic acid by partial oxidation of isobutene. The volume space velocity of the olefin relative to the catalyst is 90-200 hr-1The reaction temperature is 300-420 ℃, the absolute pressure is 0.1-0.5 Mpa, and O2The molar ratio of the water vapor to the olefin is 1-10, and the molar ratio of the water vapor to the olefin is 1-15.
In a preferred embodiment of the present invention, the propylene oxidation reaction comprises the steps of: the catalyst is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water/supplemented nitrogen is controlled to be 1:1.2-2:0.5-2:0-3, and the total space velocity is 800--1. The reaction temperature is 300-; after 90-120 hours of reaction, the propylene conversion, acrolein and acrylic acid yields and carbon oxide yields were again determined.
When the catalyst obtained by the method is used for propylene oxidation reaction, the conversion rate of propylene can exceed 98 percent (the conversion rate of the propylene of the catalyst prepared by the prior method is generally lower than 98 percent), the yield of propylene oxidation products exceeds 94 percent (the yield of the propylene oxidation products of the catalyst prepared by the prior method is generally about 90 percent), and the amount of carbon oxide byproducts is lower than 3 percent (the amount of the carbon oxide byproducts of the catalyst prepared by the prior method is generally higher than 3.5 percent).
Another aspect of the present invention relates to a method for preparing the composite oxide catalyst of the present invention. The specific steps of the method are as described above.
The preparation method of the composite oxide catalyst is characterized in that a special roasting process is adopted, namely the catalyst is firstly roasted in an inert atmosphere or an atmosphere with certain concentration of reducing gas and then is roasted in oxygen or air to obtain the finished catalyst. The catalyst provided by the method not only improves the activity of the catalyst, but also inhibits the generation of carbon monoxide and carbon dioxide, improves the selectivity of the catalyst, reduces the activity reduction rate of the catalyst and improves the stability of the catalyst.
The present invention is further described by the following examples, but the scope of protection is not limited by the examples.
Examples
1. Evaluation of catalyst Activity:
the propylene conversion and acrolein and acrylic acid yields were calculated using the following equations:
propylene conversion (mol%) =100 × (moles of propylene supplied-moles of propylene remaining after reaction)/moles of propylene supplied
Yield of acrolein and acrylic acid (mol%) =100 × (mol number of acrolein and acrylic acid formed by reaction)/mol number of propylene supplied
The yield of carbon oxide (mol%) was 100 × (moles of carbon oxide produced by the reaction)/moles of propylene supplied.
Example 1
Preparation of the catalyst
3000mL of water was heated to 60 ℃ and 1421.6g of ammonium molybdate, 6.1g of potassium nitrate and 3.6g of sodium nitrate were added thereto, followed by stirring to dissolve them to obtain a solution (1) and the temperature was maintained at 70 ℃.
Heating 1300mL of water to 50 ℃, sequentially adding 1003.1g of cobalt nitrate, 443.3g of nickel nitrate, 482.0g of ferric nitrate and 250.4g of lanthanum nitrate, stirring and dissolving, adding 30mL of nitric acid and 550.0g of bismuth nitrate, stirring and dissolving to obtain a solution (2), and keeping the temperature at 50-70 ℃.
300ml of ammonia water was prepared. While stirring vigorously at 70 deg.C, the solution (2) was dropped into the solution (1), while ammonia water was added to maintain the pH of the slurry at 1.5. The slurry was dried at 145 ℃ for 24 hours, and the dried sample was pulverized and calcined at 210 ℃ for 15 hours. The obtained powder material and silicon powder are uniformly mixed according to the weight ratio of 7:3, and 3 percent of graphite and 2 percent of SiO (SiO) by weight of the mixture are added2Content) silica sol, and tabletting to obtain hollow cylindrical granules with an outer diameter of 5mm, an inner diameter of 2mm and a length of 3 mm.
And sequentially carrying out the following roasting treatment on the obtained molded catalyst to obtain the catalyst:
(i) calcining at 425 ℃ for 5 hours in a low oxidizing atmosphere containing 10 volume percent ammonia, 17.8 volume percent oxygen, and the balance nitrogen;
(ii) the resulting product was calcined at 510 ℃ for 5 hours in an oxidizing atmosphere containing 21 vol% oxygen and the balance nitrogen.
Evaluation of catalyst Performance
50 g of the catalyst prepared above is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water/supplemented nitrogen is 1:1.6:1.5, and the total space velocity is 1000h-1. The reaction temperature was 330 ℃.
After 2 hours of reaction, the propylene conversion was determined to be 98.3%, the acrolein and acrylic acid yields were 94.2%, and the carbon oxide yield was determined to be 2.7%;
after 96 hours of reaction, the propylene conversion was 98.2%, the acrolein and acrylic acid yields were 94.0%, and the carbon oxide yield was 2.6%.
Example 2
Preparation of the catalyst
4000mL of water was heated to 60 ℃ and 1561.6g of ammonium molybdate, 36.5g of ammonium paratungstate, 7.1g of potassium nitrate and 325.5g of basic bismuth nitrate were added thereto, and the mixture was dissolved by stirring to obtain a solution (1) at a temperature of 70 ℃.
Heating 1300mL of water to 50 ℃, sequentially adding 1399.1g of cobalt nitrate, 523.3g of nickel nitrate, 484.0g of ferric nitrate and 41.5g of cerium nitrate, stirring and dissolving, then adding 30mL of nitric acid and 125.0g of bismuth nitrate, stirring and dissolving to obtain a solution (2), and keeping the temperature at 50-70 ℃.
Dropping the solution (2) into the solution (1) under vigorous stirring at 70 ℃. The slurry was dried at 145 ℃ for 24 hours, and the dried sample was pulverized and calcined at 210 ℃ for 15 hours. The obtained powder material and silicon powder are uniformly mixed according to the weight ratio of 7:3, and 3 percent of graphite and 2 percent of SiO (SiO) by weight of the mixture are added2Content) mixing silica sol, extruding into strips, and forming into particles with the diameter of 1mm and the length of 1-2 mm.
And sequentially carrying out the following roasting treatment on the obtained molded catalyst to obtain the catalyst:
(i) calcining at 440 deg.C in a low oxidizing atmosphere for 6 hours under a calcining gas containing 8.1 vol.% acrolein, 13.5 vol.% oxygen, and the balance nitrogen;
(ii) the resulting mixture was further calcined at 515 ℃ for 8 hours in an oxidizing atmosphere containing 21 vol% oxygen and the balance nitrogen.
Evaluation of catalyst Performance
50 g of the catalyst prepared above is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water is 1:1.6:1.5, and the total space velocity is 1300h-1. The reaction temperature was 325 ℃.
After reacting for 2 hours, the conversion rate of propylene is 98.4 percent, the yield of acrolein and acrylic acid is 94.3 percent, and the yield of carbon oxide is 2.6 percent;
after 96 hours of reaction, the conversion rate of propylene was 98.5%, the yield of acrolein and acrylic acid was 94.3%, and the yield of carbon oxide was 2.7%.
Example 3
Preparation of the catalyst
3000mL of water was heated to 60 ℃ and 1421.6g of ammonium molybdate, 6.1g of potassium nitrate and 3.6g of sodium nitrate were added thereto, followed by stirring to dissolve them to obtain a solution (1) and the temperature was maintained at 70 ℃.
Heating 1300mL of water to 50 ℃, sequentially adding 1003.1g of cobalt nitrate, 443.3g of nickel nitrate, 482.0g of ferric nitrate and 250.4g of lanthanum nitrate, stirring and dissolving, adding 30mL of nitric acid and 550.0g of bismuth nitrate, stirring and dissolving to obtain a solution (2), and keeping the temperature at 50-70 ℃.
300ml of ammonia water was prepared. While stirring vigorously at 70 deg.C, the solution (2) was dropped into the solution (1), while ammonia water was added to maintain the pH of the slurry at 2.0. The slurry was dried at 145 ℃ for 24 hours, and the dried sample was pulverized and calcined at 210 ℃ for 15 hours. The obtained powder material is uniformly mixed with silicon powder according to the proportion of 7:3, and 3 percent of graphite and 2 percent of SiO (SiO) by weight of the mixture are added2Content) silica sol, and tabletting to obtain hollow cylindrical granules with an outer diameter of 5mm, an inner diameter of 2mm and a length of 3 mm.
And (3) sequentially roasting the formed catalyst to obtain the catalyst:
(i) calcining at 465 deg.C for 2 hours in a low oxidizing atmosphere containing 6.2 volume percent hydrogen and the balance helium;
(ii) the resulting product was calcined at 513 ℃ for 5 hours in an oxidizing atmosphere containing 30 vol% oxygen and the balance helium.
Evaluation of catalyst Performance
50 g of the catalyst prepared above is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water/supplemented nitrogen is 1:1.6:1.5, and the total space velocity is 1000h-1. The reaction temperature was 330 ℃.
50 g of the catalyst prepared above is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water is 1:1.6:1.5, and the total space velocity is 1300h-1. The reaction temperature was 332 ℃.
After reacting for 2 hours, the conversion rate of propylene is 98.4 percent, the yield of acrolein and acrylic acid is 94.0 percent, and the yield of carbon oxide is 2.7 percent;
after 96 hours of reaction, the conversion of propylene was 98.5%, the yield of acrolein and acrylic acid was 94.1%, and the yield of carbon oxide was 2.6%.
Example 4
Preparation of the catalyst
4000mL of water was heated to 60 ℃ and 1561.6g of ammonium molybdate, 36.5g of ammonium paratungstate, 7.1g of potassium nitrate and 325.5g of basic bismuth nitrate were added thereto, and the mixture was dissolved by stirring to obtain a solution (1) at a temperature of 70 ℃.
Heating 1300mL of water to 50 ℃, sequentially adding 1399.1g of cobalt nitrate, 523.3g of nickel nitrate, 484.0g of ferric nitrate and 41.5g of cerium nitrate, stirring and dissolving, then adding 30mL of nitric acid and 125.0g of bismuth nitrate, stirring and dissolving to obtain a solution (2), and keeping the temperature at 50-70 ℃.
Dropping the solution (2) into the solution (1) under vigorous stirring at 70 ℃. Drying the slurry at 145 deg.C for 24 hr, pulverizing the dried sampleCalcining at 210 deg.C for 15 hr. The obtained powder material and silicon powder are uniformly mixed according to the weight ratio of 7:3, and 3 percent of graphite and 2 percent of SiO (SiO) by weight of the mixture are added2Content) mixing silica sol, extruding into strips, and forming into particles with the diameter of 1mm and the length of 1-2 mm.
And (3) sequentially roasting the formed catalyst to obtain the catalyst:
(i) calcining at 480 ℃ for 3 hours in a low oxidizing atmosphere containing 12 vol% propylene, 12 vol% water vapor and the balance nitrogen;
(ii) the resulting mixture was further calcined at 512 ℃ for 5 hours in an oxidizing atmosphere containing 25% by volume of oxygen and the balance argon.
Evaluation of catalyst Performance
50 g of the catalyst prepared above is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water is 1:1.6:1.5, and the total space velocity is 1300h-1. The reaction temperature was 331 ℃.
After reacting for 2 hours, the conversion rate of propylene is 98.5 percent, the yield of acrolein and acrylic acid is 94.2 percent, and the yield of carbon oxide is 2.6 percent;
after 96 hours of reaction, the conversion of propylene was 98.5%, the yield of acrolein and acrylic acid was 94.3%, and the yield of carbon oxide was 2.5%.
Example 5
Preparation of the catalyst
4000mL of water was heated to 60 ℃ and 1561.6g of ammonium molybdate, 36.5g of ammonium paratungstate, 7.1g of potassium nitrate and 325.5g of basic bismuth nitrate were added thereto, and the mixture was dissolved by stirring to obtain a solution (1) at a temperature of 70 ℃.
Heating 1300mL of water to 50 ℃, sequentially adding 1399.1g of cobalt nitrate, 523.3g of nickel nitrate, 484.0g of ferric nitrate and 41.5g of cerium nitrate, stirring and dissolving, then adding 30mL of nitric acid and 125.0g of bismuth nitrate, stirring and dissolving to obtain a solution (2), and keeping the temperature at 50-70 ℃.
Dropping the solution (2) into the solution (1) under vigorous stirring at 70 ℃. The slurry was dried at 145 ℃ for 24 hours, and the dried sample was pulverized and calcined at 210 ℃ for 15 hours. The obtained powder is mixed with silicon uniformly according to the proportion of 7:3, and 3 percent of graphite and 2 percent of SiO (SiO) by weight of the mixture are added2Content) mixing silica sol, extruding into strips, and forming into particles with the diameter of 1mm and the length of 1-2 mm.
The formed catalyst is sequentially roasted to prepare the catalyst:
(i) calcining at 485 ℃ for 5 hours in a low oxidizing atmosphere containing 25% by volume ammonia, 13.5% by volume oxygen, and the balance nitrogen;
(ii) the resulting mixture was further calcined at 515 ℃ for 5 hours in an oxidizing atmosphere containing 21 vol% oxygen and the balance nitrogen.
Evaluation of catalyst Performance
50 g of the catalyst prepared above is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water is 1:1.6:1.5, and the total space velocity is 1300h-1. The reaction temperature was 336 ℃.
After reacting for 2 hours, the conversion rate of propylene is 98.2 percent, the yield of acrolein and acrylic acid is 93.9 percent, and the yield of carbon oxide is 2.8 percent;
after 96 hours of reaction, the conversion of propylene was 98.5%, the yield of acrolein and acrylic acid was 94.4%, and the yield of carbon oxide was 2.5%.
Example 6
Preparation of the catalyst
4500ml of water was heated to 75 ℃ and 1312.6g of ammonium molybdate and 8.1g of potassium nitrate were added thereto, followed by stirring to dissolve them to obtain a solution (1) and the temperature was maintained at 75 ℃.
Heating 1300ml of water to 70 ℃, adding 1050.4g of cobalt nitrate, 514.6g of nickel nitrate and 546.6g of ferric nitrate, stirring for dissolution, adding 50ml of nitric acid and 470.1g of bismuth nitrate, stirring for dissolution to obtain a solution (2), and keeping the temperature at 65 ℃.
Dropping the solution (2) into the solution (1) within 10 minutes under the condition of vigorous stirring at 70 ℃, simultaneously adding 10% urea aqueous solution to keep the pH value of the slurry to be 1.6, and continuously stirring until the solution is uniformly mixed after the addition is finished. The slurry was spray dried at 180 ℃ and treatment continued at 210 ℃ for 15 hours. A composite oxide powder sample was obtained.
Mixing the obtained composite oxide powder sample with silicon powder according to the weight ratio of 7:3, adding 3% of graphite and 2% (SiO)2Content) silica sol, and flaking and molding into cylindrical hollow particles with an outer diameter of 5mm, an inner diameter of 2mm and a length of 3 mm.
The formed catalyst is sequentially roasted to prepare the catalyst:
(i) calcining at 460 ℃ for 5 hours in a low oxidizing atmosphere containing 10 vol.% acrolein, 15.5 vol.% oxygen, and the balance nitrogen;
(ii) the resulting mixture was further calcined at 515 ℃ for 10 hours in an oxidizing atmosphere containing 21 vol% oxygen and the balance nitrogen.
Evaluation of catalyst Performance
50 g of catalyst is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air, steam and nitrogen is introduced, the molar ratio of propylene/oxygen/water/supplemented nitrogen is 1:1.8:2.5:2.5, and the total space velocity is 1850h-1. The reaction temperature was 332 ℃.
After reacting for 2 hours, the conversion rate of propylene is 98.8 percent, the yield of acrolein and acrylic acid is 93.8 percent, and the yield of carbon oxide is 2.8 percent;
after 96 hours of reaction, the conversion of propylene was 98.8%, the yield of acrolein and acrylic acid was 94.1%, and the yield of carbon oxide was 2.5%.
Comparative example 1
Preparation of the catalyst
3000mL of water was heated to 60 ℃ and 1421.6g of ammonium molybdate, 6.1g of potassium nitrate and 3.6g of sodium nitrate were added thereto, followed by stirring to dissolve them to obtain a solution (1) and the temperature was maintained at 70 ℃.
Heating 1300mL of water to 50 ℃, sequentially adding 1003.1g of cobalt nitrate, 443.3g of nickel nitrate, 482.0g of ferric nitrate and 250.4g of lanthanum nitrate, stirring and dissolving, adding 30mL of nitric acid and 550.0g of bismuth nitrate, stirring and dissolving to obtain a solution (2), and keeping the temperature at 50-70 ℃.
300ml of ammonia water was prepared. While stirring vigorously at 70 deg.C, the solution (2) was dropped into the solution (1), while ammonia water was added to maintain the pH of the slurry at 2.0. The slurry was dried at 145 ℃ for 24 hours, and the dried sample was pulverized and calcined at 210 ℃ for 15 hours. The obtained powder material and silicon powder are uniformly mixed according to the weight ratio of 7:3, and 3 percent of graphite and 2 percent of SiO (SiO) by weight of the mixture are added2Content) silica sol, and tabletting to obtain hollow cylindrical granules with an outer diameter of 5mm, an inner diameter of 2mm and a length of 3 mm.
The shaped catalyst was calcined at 510 ℃ for 5 hours at 510 ℃ in an oxidizing atmosphere containing 21% by volume oxygen and the balance nitrogen to produce the catalyst.
Evaluation of catalyst Performance
50 g of the catalyst prepared above is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water/supplemented nitrogen is 1:1.6:1.5, and the total space velocity is 1000h-1. The reaction temperature was 335 ℃.
After 2 hours of reaction, the propylene conversion was found to be 97.5%, the acrolein and acrylic acid yields were found to be 91.7%, and the carbon oxide yield was found to be 3.6%;
after 96 hours of reaction, the propylene conversion was 96.5%, the acrolein and acrylic acid yields 90.5%, and the carbon oxide yield 3.6% were measured.
Comparative example 2
Preparation of the catalyst
4000mL of water was heated to 60 ℃ and 1561.6g of ammonium molybdate, 36.5g of ammonium paratungstate, 7.1g of potassium nitrate and 325.5g of basic bismuth nitrate were added thereto, and the mixture was dissolved by stirring to obtain a solution (1) at a temperature of 70 ℃.
Heating 1300mL of water to 50 ℃, sequentially adding 1399.1g of cobalt nitrate, 523.3g of nickel nitrate, 484.0g of ferric nitrate and 41.5g of cerium nitrate, stirring and dissolving, then adding 30mL of nitric acid and 125.0g of bismuth nitrate, stirring and dissolving to obtain a solution (2), and keeping the temperature at 50-70 ℃.
Dropping the solution (2) into the solution (1) under vigorous stirring at 70 ℃. The slurry was dried at 145 ℃ for 24 hours, and the dried sample was pulverized and calcined at 210 ℃ for 15 hours. The obtained powder material and silicon powder are uniformly mixed according to the weight ratio of 7:3, and 3 percent of graphite and 2 percent of SiO (SiO) by weight of the mixture are added2Content) mixing silica sol, extruding into strips, and forming into particles with the diameter of 1mm and the length of 1-2 mm.
The shaped catalyst was calcined at 515 ℃ for 8 hours in an oxidizing atmosphere containing 21% by volume of oxygen and the balance nitrogen.
Evaluation of catalyst Performance
50 g of the catalyst prepared above is loaded into a fixed bed tubular reactor, preheated mixed gas of propylene, air and steam is introduced, the molar ratio of propylene/oxygen/water is 1:1.6:1.5, and the total space velocity is 1300h-1. The reaction temperature was 358 ℃.
After reacting for 2 hours, the conversion rate of propylene is 97.8 percent, the yield of acrolein and acrylic acid is 92.4 percent, and the yield of carbon oxide is 3.8 percent;
after 96 hours of reaction, the conversion of propylene was 96.1%, the yield of acrolein and acrylic acid was 91.5%, and the yield of carbon oxide was 3.7%.
It can be seen from the above examples that the two-stage roasting according to the present invention can increase the conversion rate of propylene and reduce the yield of carbon oxide, thereby advantageously increasing the productivity of the oxidation reaction of propylene, as compared with the one-time roasting in an oxidizing atmosphere.
Claims (10)
1. A catalyst having the general formula:
Mo12BibFecCodXeYfZgOi，
wherein,
x is at least one element selected from the group consisting of W, Sb, As, P, Ni, Sn, Ce and Pb;
y is at least one element selected from Zn, Cr, Mn, Ru, Ag, Pd and La;
z is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr, and Ba;
b is 0.1 to 7;
c is 0.5 to 8;
d is 1 to 6;
e is 0.1 to 3;
f is 0 to 1;
g is 0-2;
h is a number determined by the oxidation state of each of the above elements;
the method is characterized in that the catalyst is prepared by the following method:
(i) providing precursors of the elements, and obtaining a formed catalyst by mixing, pre-roasting, coating on an inert carrier or directly forming;
(ii) roasting the obtained molded catalyst for 3-20 hours at 380-520 ℃ in inert gas or atmosphere containing at least 5-40% of ammonia gas, hydrogen gas, propylene, acrolein, 0-19% of molecular oxygen and the balance of inert gas; and
(iii) roasting the mixture for 3 to 24 hours at the temperature of 450 to 540 ℃ in an atmosphere containing 21 to 35 percent of molecular oxygen, wherein the volume space velocity of the roasting gas relative to the catalyst is 50 to 2000 hours-1Thus obtaining the catalyst.
2. The catalyst of claim 1, wherein X is at least one element selected from the group consisting of W, Ce and Ni;
y is at least one element selected from La, Cr and Ru;
z is at least one element selected from Na and K;
b is 1 to 6, preferably 2 to 5;
c is 1 to 6, preferably 2 to 5;
d is 2 to 5, preferably 3 to 4;
e is 0.5 to 2.5, preferably 0.8 to 2;
f is 0.2 to 0.8, preferably 0.4 to 0.6;
g is 0.2 to 1.8, preferably 0.5 to 1.5;
h is a number determined by the oxidation state of each element described above.
3. The catalyst according to claim 1 or 2, characterized in that the precursor of each element is a nitrate of each element; the molded catalyst has a solid or hollow shape selected from a sphere, a cylinder, a clover, a gear, etc., and is formed by molding the composite catalyst itself or coating the composite oxide catalyst on a catalyst carrier having the above shape.
4. A catalyst according to any one of claims 1 to 3, characterised in that step (i) comprises the steps of:
(a) dissolving nitrate precursor of molybdenum, X, Y or Z in water to obtain solution (1);
(b) dissolving nitrate precursors of Fe, Co and Ni in water, adding nitrate precursors of nitric acid and Bi, and adding X, Y or Z nitrate precursors to obtain a solution (2);
(c) mixing the solutions (1) and (2) to obtain slurry, and drying the slurry at the temperature of 100-160 ℃;
(d) pre-roasting the obtained dry product at the temperature of 180-280 ℃;
(e) adding 0-50% of diluent heat-conducting agent, 0.01-10% of binder and 0.01-8% of lubricant into the pre-roasted product, uniformly mixing, and coating on solid or hollow inert carriers such as spherical, cylindrical, clover-shaped, gear-shaped and the like, or directly forming into the specific shape to obtain the formed catalyst.
5. The catalyst of any one of claims 1 to 4, wherein the molecular oxygen content in the calcining atmosphere of step (ii) is from 0 to 19% by volume, the balance being non-oxygen gas selected from one or more of the following: 5 to 40 volume percent of ammonia, hydrogen, propylene, acrolein, nitrogen, argon and helium;
preferably, the amount of molecular oxygen detectable in the firing atmosphere is less than or equal to 5 vol%, preferably less than or equal to 3 vol%, more preferably less than or equal to 1 vol%, with the balance being the non-oxygen gas.
6. The catalyst of any of claims 1 to 5, wherein the shaped catalyst has a calcination atmosphere selected from the group consisting of:
(i) an atmosphere comprising 0-19% by volume of molecular oxygen, 5-40% by volume of ammonia gas and the balance of nitrogen gas;
(ii) an atmosphere comprising 0-19% by volume of molecular oxygen, 5-40% by volume of ammonia gas and the balance of nitrogen gas; or
(iii) An atmosphere comprising acrolein, 0-19% by volume of molecular oxygen and nitrogen.
7. The catalyst according to any one of claims 1 to 6, characterized in that the calcination temperature of the shaped catalyst is 400-480 ℃, preferably 420-460 ℃; the calcination time is 3 to 24 hours, preferably 5 to 16 hours.
8. A method according to any of claims 1 to 7, wherein in step (iii) the calcination is carried out in an atmosphere comprising 21% to 33% molecular oxygen and the balance inert gas, more preferably in an atmosphere comprising 21% to 30% molecular oxygen and the balance inert gas.
9. The process according to any of claims 1 to 8, characterized in that in step (iii) the calcination is carried out at a temperature of 450 ℃ and 520 ℃, preferably at a temperature of 460 ℃ and 510 ℃ for a period of 5 to 18 hours, preferably 6 to 15 hours.
10. A process for the preparation of a catalyst having the general formula:
Mo12BibFecCodXeYfZgOi，
wherein,
x is at least one element selected from the group consisting of W, Sb, As, P, Ni, Sn, Ce and Pb;
y is at least one element selected from Zn, Cr, Mn, Ru, Ag, Pd and La;
z is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr, and Ba;
b is 0.1 to 7;
c is 0.5 to 8;
d is 1 to 6;
e is 0.1 to 3;
f is 0 to 1;
g is 0-2;
h is a number determined by the oxidation state of each of the above elements;
it comprises the following steps:
(i) providing precursors of the elements, and obtaining a formed catalyst by mixing, pre-roasting, coating on an inert carrier or directly forming;
(ii) roasting the obtained molded catalyst for 3-20 hours at 380-520 ℃ in an atmosphere containing at least 5-40% of ammonia gas, hydrogen gas, propylene, acrolein, 0-19% of molecular oxygen and the balance of inert gas; and
(iii) roasting for 3-20 hours at 450-540 ℃ in an atmosphere containing 21-35% of molecular oxygen, wherein the volume space velocity of roasting gas relative to the catalyst is 50-2000 h-1Thus obtaining the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210382522.3A CN103721722B (en) | 2012-10-10 | 2012-10-10 | Composite oxide catalysts and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210382522.3A CN103721722B (en) | 2012-10-10 | 2012-10-10 | Composite oxide catalysts and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103721722A true CN103721722A (en) | 2014-04-16 |
| CN103721722B CN103721722B (en) | 2017-03-08 |
Family
ID=50446161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210382522.3A Active CN103721722B (en) | 2012-10-10 | 2012-10-10 | Composite oxide catalysts and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103721722B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801312A (en) * | 2015-03-17 | 2015-07-29 | 烟台大学 | Composite oxide catalyst and preparation method |
| CN105435805A (en) * | 2014-08-18 | 2016-03-30 | 上海华谊新材料有限公司 | Catalyst and method and reaction system for production of acrylic acid by use of catalyst |
| CN105772013A (en) * | 2014-12-25 | 2016-07-20 | 上海华谊新材料有限公司 | Composite multi-metal oxide catalyst and preparation method thereof |
| CN106582677A (en) * | 2016-12-01 | 2017-04-26 | 万华化学集团股份有限公司 | Preparation method and application of polymetallic composite oxide catalyst |
| CN106748590A (en) * | 2016-12-21 | 2017-05-31 | 四川雅化实业集团股份有限公司 | A kind of viscous explosive adhesive and preparation method thereof |
| CN106881103A (en) * | 2015-12-15 | 2017-06-23 | 上海华谊新材料有限公司 | The application method of composite oxide catalysts |
| CN106881101A (en) * | 2015-12-15 | 2017-06-23 | 上海华谊新材料有限公司 | Composite oxide catalysts and its production and use |
| CN109529862A (en) * | 2018-11-28 | 2019-03-29 | 中山大学 | A kind of nano-hollow microspherical catalyst prepares the application in methacrylaldehyde in propylene oxidation |
| CN111744497A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Ammonia oxidation catalyst particles, and preparation method and application thereof |
| CN112547043A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing acrylic acid from acrolein and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080284A (en) * | 1990-03-19 | 1994-01-05 | 标准石油公司 | Method and the catalyzer of the ammonoxidating propylene to produce acrylonitrile that has improved |
| CN1143946A (en) * | 1994-06-22 | 1997-02-26 | 旭化成工业株式会社 | Process for producing methacrolein |
| JPH10216523A (en) * | 1997-01-31 | 1998-08-18 | Asahi Chem Ind Co Ltd | Catalyst for producing metacrolein and production of metacrolein |
| CN1282630A (en) * | 1999-05-25 | 2001-02-07 | 株式会社日本触媒 | Compound oxide catalyst and method for preparing (methyl) propenal and (methgl) acrylic acid |
| CN1462210A (en) * | 2000-09-21 | 2003-12-17 | 巴斯福股份公司 | Method for producing multi-metal oxide catalyst, method for producing unsaturated aldehydes and/or carhoxylicacids and band calcination device |
| CN1596149A (en) * | 2001-12-21 | 2005-03-16 | 旭化成化学株式会社 | Oxide catalyst composition |
| CN1647853A (en) * | 2004-11-26 | 2005-08-03 | 上海华谊丙烯酸有限公司 | Catalyst for the selective oxidation of tert-butanol or isobutene to methacrolein and its application |
| JP2007044668A (en) * | 2005-08-12 | 2007-02-22 | Nippon Kayaku Co Ltd | Method for producing composite metal oxide catalyst and application of the catalyst |
| CN1939589A (en) * | 2005-09-30 | 2007-04-04 | 住友化学株式会社 | Preparing method of catalyst for preparing unsaturated aldehyde and unsaturated carboxylic acid and preparing method of unsaturated aldehyde and unsaturated carboxylic acid |
| CN101579630A (en) * | 2008-05-16 | 2009-11-18 | 住友化学株式会社 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
-
2012
- 2012-10-10 CN CN201210382522.3A patent/CN103721722B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080284A (en) * | 1990-03-19 | 1994-01-05 | 标准石油公司 | Method and the catalyzer of the ammonoxidating propylene to produce acrylonitrile that has improved |
| CN1143946A (en) * | 1994-06-22 | 1997-02-26 | 旭化成工业株式会社 | Process for producing methacrolein |
| JPH10216523A (en) * | 1997-01-31 | 1998-08-18 | Asahi Chem Ind Co Ltd | Catalyst for producing metacrolein and production of metacrolein |
| CN1282630A (en) * | 1999-05-25 | 2001-02-07 | 株式会社日本触媒 | Compound oxide catalyst and method for preparing (methyl) propenal and (methgl) acrylic acid |
| CN1462210A (en) * | 2000-09-21 | 2003-12-17 | 巴斯福股份公司 | Method for producing multi-metal oxide catalyst, method for producing unsaturated aldehydes and/or carhoxylicacids and band calcination device |
| CN1596149A (en) * | 2001-12-21 | 2005-03-16 | 旭化成化学株式会社 | Oxide catalyst composition |
| CN1647853A (en) * | 2004-11-26 | 2005-08-03 | 上海华谊丙烯酸有限公司 | Catalyst for the selective oxidation of tert-butanol or isobutene to methacrolein and its application |
| JP2007044668A (en) * | 2005-08-12 | 2007-02-22 | Nippon Kayaku Co Ltd | Method for producing composite metal oxide catalyst and application of the catalyst |
| CN1939589A (en) * | 2005-09-30 | 2007-04-04 | 住友化学株式会社 | Preparing method of catalyst for preparing unsaturated aldehyde and unsaturated carboxylic acid and preparing method of unsaturated aldehyde and unsaturated carboxylic acid |
| CN101579630A (en) * | 2008-05-16 | 2009-11-18 | 住友化学株式会社 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435805B (en) * | 2014-08-18 | 2018-03-23 | 上海华谊新材料有限公司 | Catalyst, with the Catalyst Production acrylic acid and reaction system |
| CN105435805A (en) * | 2014-08-18 | 2016-03-30 | 上海华谊新材料有限公司 | Catalyst and method and reaction system for production of acrylic acid by use of catalyst |
| CN105772013A (en) * | 2014-12-25 | 2016-07-20 | 上海华谊新材料有限公司 | Composite multi-metal oxide catalyst and preparation method thereof |
| CN104801312A (en) * | 2015-03-17 | 2015-07-29 | 烟台大学 | Composite oxide catalyst and preparation method |
| CN106881101B (en) * | 2015-12-15 | 2020-06-23 | 上海华谊新材料有限公司 | Composite oxide catalyst, preparation method and application thereof |
| CN106881103A (en) * | 2015-12-15 | 2017-06-23 | 上海华谊新材料有限公司 | The application method of composite oxide catalysts |
| CN106881101A (en) * | 2015-12-15 | 2017-06-23 | 上海华谊新材料有限公司 | Composite oxide catalysts and its production and use |
| CN106582677A (en) * | 2016-12-01 | 2017-04-26 | 万华化学集团股份有限公司 | Preparation method and application of polymetallic composite oxide catalyst |
| CN106582677B (en) * | 2016-12-01 | 2019-04-23 | 万华化学集团股份有限公司 | A kind of preparation method and its usage of more metal composite oxide catalysts |
| CN106748590A (en) * | 2016-12-21 | 2017-05-31 | 四川雅化实业集团股份有限公司 | A kind of viscous explosive adhesive and preparation method thereof |
| CN109529862A (en) * | 2018-11-28 | 2019-03-29 | 中山大学 | A kind of nano-hollow microspherical catalyst prepares the application in methacrylaldehyde in propylene oxidation |
| CN111744497A (en) * | 2019-03-28 | 2020-10-09 | 中国石油化工股份有限公司 | Ammonia oxidation catalyst particles, and preparation method and application thereof |
| CN111744497B (en) * | 2019-03-28 | 2023-07-07 | 中国石油化工股份有限公司 | Ammonia oxidation catalyst particles, manufacturing method and application thereof |
| CN112547043A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing acrylic acid from acrolein and preparation method and application thereof |
| CN112547043B (en) * | 2019-09-25 | 2023-03-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing acrylic acid from acrolein and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103721722B (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103721722B (en) | Composite oxide catalysts and preparation method thereof | |
| US8481790B2 (en) | Catalyst for producing unsaturated aldehyde by oxidation of lower olefin at high space velocity | |
| JP6294883B2 (en) | Process for producing unsaturated aldehyde and / or unsaturated carboxylic acid | |
| US7132384B2 (en) | Process for producing composite oxide catalyst | |
| JP5919870B2 (en) | Method for producing acrylonitrile production catalyst and method for producing acrylonitrile using the acrylonitrile production catalyst | |
| KR101776796B1 (en) | Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid, method for manufacturing same, and method for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid | |
| KR102422025B1 (en) | Catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid and manufacturing method of same, and manufacturing method of unsaturated aldehyde and/or unsaturated carboxylic acid | |
| KR101819465B1 (en) | Method for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid | |
| EP1867387B1 (en) | Method for manufacturing a catalyst for use in the production of methacrylic acid | |
| JP4954750B2 (en) | Method for producing molybdenum, bismuth, iron, silica-containing composite oxide catalyst | |
| CN101992093A (en) | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity | |
| JPWO2004073857A1 (en) | Catalyst for producing methacrylic acid and process for producing the same | |
| KR102612311B1 (en) | Method for producing acrolein, methacrolein, acrylic acid or methacrylic acid | |
| JP5793345B2 (en) | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid | |
| JP2005169311A (en) | Production method for complex oxide catalyst | |
| JP2005161309A (en) | Method for producing composite oxide catalyst | |
| JP3772389B2 (en) | Method for producing oxidation catalyst and method for producing methacrylic acid | |
| CN102989470A (en) | Catalyst for preparing unsaturated aldehyde by oxidizing low-carbon olefin and preparation method thereof | |
| WO2016147324A1 (en) | Catalyst for production of unsaturated aldehyde and/or unsaturated carboxylic acid, method for producing same, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid | |
| JP6238354B2 (en) | Catalyst for producing unsaturated aldehyde and / or unsaturated carboxylic acid, method for producing the same, and method for producing unsaturated aldehyde and / or unsaturated carboxylic acid | |
| US20220177401A1 (en) | Method for producing a catalyst for unsaturated carboxylic acid synthesis | |
| JP2009095713A (en) | Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid | |
| JP2011050839A (en) | Catalyst and method for producing methacrolein and methacrylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190212 Address after: Room 357, No. 100, Lane 295, Canggong Road, Fengxian District, Shanghai, 201424 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: No. 2031 Pudong Road, Pudong New Area, Shanghai, 2003 Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |