CN111434381A - Catalyst for producing acrolein and/or acrylic acid and method for producing same - Google Patents
Catalyst for producing acrolein and/or acrylic acid and method for producing same Download PDFInfo
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- CN111434381A CN111434381A CN201910026650.6A CN201910026650A CN111434381A CN 111434381 A CN111434381 A CN 111434381A CN 201910026650 A CN201910026650 A CN 201910026650A CN 111434381 A CN111434381 A CN 111434381A
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 190
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 36
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 66
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010703 silicon Substances 0.000 claims abstract description 59
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 51
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 30
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000011733 molybdenum Substances 0.000 claims abstract description 27
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 8
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- 229910052788 barium Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910020630 Co Ni Inorganic materials 0.000 claims abstract description 6
- 229910002440 Co–Ni Inorganic materials 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 25
- 239000004480 active ingredient Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 35
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 14
- 125000004429 atom Chemical group 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 230000009471 action Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 8
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 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 5
- 239000000463 material Substances 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 235000010333 potassium nitrate Nutrition 0.000 description 5
- 239000004323 potassium nitrate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 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 4
- 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 4
- 239000013589 supplement Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 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 3
- 230000020169 heat generation Effects 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000975 co-precipitation Methods 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
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8878—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention provides a catalyst for producing acrolein and/or acrylic acid and a method for producing the same. The catalyst takes silicon spheres as a carrier and has an internal and external double-layer coating, wherein the internal layer contains molybdenum oxide, and the external layer contains Mo-Bi-Fe-Co-Ni compositeAn oxide active component having Mo12BiaFebCocNidXeYfOgThe general formula is shown in the specification, wherein X is at least one selected from W, Sb, Zn, Cr, Mn, Sn, Si and Ce; y is at least one selected from Na, K, Rb, Cs, Mg, Ca and Ba; a. b, c, d, e and f respectively represent the number of atoms of Bi, Fe, Co, Ni, X and Y, a is 0.1-2.0, b is 0.1-5, c is 1-20, d is 1-20, e is 0-3, f is 0.01-1.0, and g is the number of oxygen atoms satisfying the valence of the oxide. The catalyst of the present invention solves the problems of heat increment caused by hot spots and molybdenum component loss under the action of high temperature water vapor in propylene oxidation reaction, has high activity, high selectivity and long service life, and is suitable for producing acrolein and/or acrylic acid.
Description
Technical Field
The present invention relates to a catalyst suitable for use in the production of acrolein and/or acrylic acid from propylene in the presence of oxygen, which catalyst is capable of solving the problem of an increase in the amount of heat generated by hot spots present in the oxidation reaction of propylene and the problem of a loss of molybdenum component by the action of high-temperature water vapor. The invention also relates to a method for producing said catalyst.
Technical Field
Many proposals have been made for catalysts for producing acrolein and acrylic acid by selective oxidation of propylene. In these schemes, basically, a composite oxide catalyst containing molybdenum, bismuth, iron and cobalt is mentioned. These catalysts are challenged by two major problems during use: the heat generated by the hot spot is increased and the molybdenum component is lost under the action of high-temperature water vapor. Both of these problems lead to a reduction in catalyst life and a decrease in selectivity.
To cope with these problems, some solutions have been proposed. For example, Japanese laid-open patent publication No. 1972-10614A mentions that the catalyst is packed in multiple layers, and each layer is diluted with inert pellets in different proportions, so as to control the hot spot of the reaction while ensuring the conversion of propylene. However, from the industrial point of view, this method has drawbacks: for example, the inert pellets and the catalyst are not mixed uniformly, hot spots still exist; the position and temperature of the hot spot of each reaction tube are different, which is inconvenient for reaction operation. Thus, this approach still presents difficulties in controlling the increase in hot spot heat generation.
Japanese patent publication No. 1988-38331B proposes that catalysts having different activities are prepared by changing the composition of the alkali metal components (K, Rb, Cs) of the catalyst, and the catalysts having different activities are respectively loaded in different layers of a reaction tube, and the activity is gradually increased from top to bottom along the reaction tube, thereby controlling the hot spot of the reaction. However, since the content of alkali metal in the catalyst is much smaller than that of other components, it causes great difficulty in catalyst preparation.
Chinese patent CN1092080C changes the forming mode of the catalyst, takes inert or porous spherical substance as a carrier, and the surface of the carrier is coated with active components to prepare the catalyst in the form of a coating. When the catalyst is used, propylene only reacts on the surface of catalyst particles, and heat can be taken away in time, so that reaction hot spots are controlled.
These solutions described above are only directed to the problem of the increase in heat generated by the hot spot of the reaction, and do not provide an effective solution to the problem of the loss of the molybdenum component during the reaction.
The Chinese patent CN102389806A provides a solution for two problems in the reaction process. It uses silicon carbide, corundum and talcum as carrier, and the catalyst layer is sprayed on the carrier. The sprayed catalyst layer is divided into an inner layer and an outer layer, wherein the inner layer is made of molybdenum oxide, and the outer layer is made of catalyst active components. The report shows that the double-layer spraying catalyst can lead the reaction heat to be taken away in time, and meanwhile, the molybdenum oxide in the inner layer can supplement the loss of the molybdenum oxide in the outer layer, so that the catalyst can keep high activity and long service life. However, the corundum or talc carrier mentioned in this patent has poor heat conductivity, and the catalyst does not take away the heat generated in the reaction well. Although the silicon carbide material has good heat-conducting property, the silicon carbide material has high hardness, so that the metal die is greatly abraded in the forming process, and impurities of components of the die belt are brought into the silicon carbide material, so that the performance of the catalyst is influenced.
Therefore, in view of the two problems of the increase of heat generation due to the hot spot existing in the oxidation reaction of propylene and the loss of the molybdenum component by the high-temperature steam, there is an urgent need for a catalyst for producing acrolein and/or acrylic acid which can solve both of these problems.
Disclosure of Invention
The invention aims to solve the technical problems that the heat generated by a hot spot is increased and the molybdenum component is lost under the action of high-temperature water vapor in the propylene oxidation reaction.
Accordingly, one aspect of the present invention relates to a catalyst for producing acrolein and/or acrylic acid by oxidation of propylene, which is a catalyst having a silica sphere as a carrier and having an inner and outer double-layered coating, the inner layer comprising molybdenum oxide and the outer layer comprising a Mo-Bi-Fe-Co-Ni composite oxide active component having a general formula represented by the following formula (1):
Mo12BiaFebCocNidXeYfOg(1)
wherein X is at least one selected from W, Sb, Zn, Cr, Mn, Sn, Si and Ce; y is at least one selected from Na, K, Rb, Cs, Mg, Ca and Ba; a. b, c, d, e, f represent the atomic number of Bi, Fe, Co, Ni, X and Y, respectively, wherein:
a＝0.1～2.0，
b＝0.1～5，
c＝1～20，
d＝1～20，
e＝0～3，
f＝0.01～1.0，
g is the number of oxygen atoms satisfying the valence of the oxide.
Another aspect of the present invention relates to a method for producing the catalyst of the present invention, which comprises the steps of:
1) providing silicon spheres, forming a molybdenum-containing coating on the surfaces of the silicon spheres, and then roasting in an oxygen-containing atmosphere to obtain the silicon spheres with the molybdenum oxide loading amount of 1-10 wt%;
2) preparing an active ingredient powder having a composition represented by the following general formula (1),
Mo12BiaFebCocNidXeYfOg(1)
wherein X is at least one selected from W, Sb, Zn, Cr, Mn, Sn, Si and Ce; y is at least one selected from Na, K, Rb, Cs, Mg, Ca and Ba; a. b, c, d, e, f represent the atomic number of Bi, Fe, Co, Ni, X and Y, respectively, wherein:
a＝0.1～2.0，
b＝0.1～5，
c＝1～20，
d＝1～20，
e＝0～3，
f＝0.01～1.0，
g is the number of oxygen atoms satisfying the valence state of the oxide;
3) preparing the obtained active component powder into slurry, arranging the slurry on the surface of a silicon sphere carrying molybdenum oxide, and then roasting to obtain the catalyst with the active component content of 15-40 wt% relative to the total weight of the catalyst.
The catalyst for producing acrolein and/or acrylic acid according to the present invention can solve the technical problems of the increase of heat generated by hot spots and the loss of molybdenum component under the action of high temperature water vapor in the propylene oxidation reaction of the prior art, and has high activity and selectivity and long service life.
According to the method for producing a catalyst of the present invention, a catalyst of the present invention having high activity, high selectivity and long life can be produced easily.
Detailed Description
The technical features of the present invention are described below in connection with preferred embodiments, which are intended to illustrate the present invention and not to limit the present invention.
[ catalyst for producing acrolein and/or acrylic acid ]
First, the structural composition of the catalyst for producing acrolein and/or acrylic acid of the present invention (hereinafter, also simply referred to as "the catalyst of the present invention") will be described.
The catalyst of the invention is a catalyst which takes silicon spheres as a carrier and has an inner and outer double-layer coating, wherein the inner layer contains molybdenum oxide, and the outer layer contains Mo-Bi-Fe-Co-Ni composite oxide active components.
The silicon ball contains a silicon material, has good heat conductivity, can take reaction heat away in time when used as a catalyst carrier, and well controls a reaction hot spot, so that the catalyst can keep high activity. In addition, the silicon ball is easy to process and manufacture, the problems of difficult processing and the like do not occur in the processing process, and the performance of the catalyst is not adversely affected in the using process.
The silicon spheres used in the invention can be prepared by adopting a physical vapor deposition method, a chemical vapor deposition method or a spray drying method.
In the present invention, the term "silicon spheres" refers to spheroidal silicon-containing materials, for example. It may be spherical, ellipsoidal, irregular, approximately spherical, or a mixture of the above shapes. The size of the silica spheres is expressed as an average diameter, and in the case of an ellipsoid, an approximately spherical shape, or the like, the average diameter refers to an equivalent diameter. The average diameter of the silicon spheres used in the present invention is 3 to 7mm, preferably 3.5 to 6.5mm, more preferably 4 to 6mm, and particularly preferably 5 mm.
In addition, the specific surface area of the silicon spheres is 5-10 m2A ratio of 5 to 8 m/g2A specific preferred range is 6 to 7m2/g。
A coating layer containing molybdenum oxide as an inner layer was formed on the surface of the silicon spheres. The method for forming the coating layer is not particularly limited, and the coating layer can be formed by a method such as dip coating or spray coating.
The content of molybdenum oxide in the coating is not particularly limited as long as molybdenum loss of the active layer at the outer layer can be effectively supplemented. In one embodiment of the present invention, the coating layer contains 60 to 100 wt% of molybdenum oxide, preferably 70 to 95 wt% of molybdenum oxide, more preferably 75 to 90 wt% of molybdenum oxide, preferably 80 to 89 wt% of molybdenum oxide, and the balance is a material that does not affect the supplement of the molybdenum loss in the outer layer and does not affect the heat dissipation of silicon, such as silicon powder, silicon oxide, silicon carbide, and the like.
In a preferred embodiment, the molybdenum oxide in the molybdenum oxide coating layer is supported in an amount of 1 to 10 wt% with respect to the silicon spheres. If the supported amount is less than the lower limit of the above range, the molybdenum oxide in the inner layer may not be able to permanently compensate for the loss of the molybdenum element in the outer catalyst layer, and the desired effect may not be obtained. The supporting amount is preferably 2 to 8% by weight, and particularly preferably 5% by weight.
The coating rate of the molybdenum oxide coating area relative to the silicon ball surface area is more than 80%. When the coating rate is within this range, the molybdenum oxide in the inner layer can promptly and uniformly supplement the loss of the molybdenum element in the external catalyst, thereby maintaining the catalyst activity. The coating rate is preferably 90% or more, more preferably 95% or more, and particularly preferably 100%.
The catalyst outer layer is formed on the molybdenum oxide coating layer and contains a Mo-Bi-Fe-Co-Ni composite oxide active component having a general formula represented by the following formula (1):
Mo12BiaFebCocNidXeYfOg(1)
wherein X is at least one selected from W, Sb, Zn, Cr, Mn, Sn, Si and Ce; y is at least one selected from Na, K, Rb, Cs, Mg, Ca and Ba; a. b, c, d, e, f represent the atomic number of Bi, Fe, Co, Ni, X and Y, respectively, wherein:
a＝0.1～2.0，
b＝0.1～5，
c＝1～20，
d＝1～20，
e＝0～3，
f＝0.01～1.0，
g is the number of oxygen atoms satisfying the valence of the oxide.
The active component of the catalyst of the present invention contains Mo, Bi, Fe, Co and Ni as essential constituent elements. Among the active components of the catalyst of the present invention, in order to obtain acrolein and/or acrylic acid at a higher conversion rate by providing the catalyst with better catalytic activity and selectivity in the propylene oxidation reaction, in the case where the number of atoms of the Mo element is 12, the number of atoms of the Bi element is preferably 0.5 to 2.0, more preferably 1.0 to 1.8, and particularly preferably 1.5 to 1.6; the number of atoms of the Fe element is preferably 0.5-3.0, more preferably 1.0-2.0, and particularly preferably 1.5-1.8; the number of atoms of the Co element is preferably 1-15, more preferably 2-10, and particularly preferably 5-8; the number of atoms of the Ni element is preferably 1 to 10, more preferably 2 to 5, and particularly preferably 2 to 3.
In addition to the above-mentioned Mo, Bi, Fe, Co and Ni, the active component of the catalyst of the invention comprises Y, Y preferably being K or Na, particularly preferably being K. When the number of Mo atoms is 12, the number of Y atoms is preferably 0.05 to 0.5, more preferably 0.1 to 0.3.
In the active component of the catalyst of the present invention, X is an optional component, and X is preferably at least one selected from W, Ce and Cr, particularly preferably Cr or W, or a combination of W and Ce. When the element X is contained, the total number of atoms of X is preferably 0.1 to 2.5, more preferably 0.2 to 2, when the number of atoms of Mo is 12.
In some preferred embodiments, Mo is exemplified as the composition of the active component of the catalyst of the present invention12Bi1.54Fe1.61Co6.53Ni2.43K0.11Ox、Mo12Bi1.54Fe1.61Co6.53Ni2.43Cr0.71K0.11Ox、Mo12Bi1.54Fe1.61Co6.53Ni2.43Cr0.35K0.11Ox、Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.20K0.11Ox、Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.30K0.1 1Ox、Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.40K0.11Ox、Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.20Ce0.94K0.11OxEtc., these active ingredients may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The catalyst having the above composition is capable of oxidizing propylene to acrolein and/or acrylic acid with high conversion and high selectivity.
In a preferred embodiment, the content of the active component is 15 to 40% by weight with respect to the catalyst. If the content of the active component is too low, the catalyst has low catalytic efficiency and short service life. If the content of the above-mentioned active ingredient is too high, the cost is increased, which is economically disadvantageous. The content of the active ingredient is more preferably 20 to 30% by weight.
The method for forming the outer layer having an active component is not particularly limited, and the outer layer can be formed on the surface of the silicon spheres supporting the molybdenum oxide coating layer by, for example, dipping, spraying, or the like. In a preferred embodiment, the powder containing the active component and the binder solution are mixed to form slurry, and the slurry is coated on the surface of the silicon spheres with the molybdenum oxide coating, so that the outer layer catalyst can be bonded on the surface of the silicon spheres, the loss of the catalytic active component is reduced, and the service life of the catalyst is prolonged.
The shape of the catalyst of the present invention includes, in addition to spherical, ellipsoidal, irregular shapes approximating spherical, or a mixture of the above shapes. The size of the catalyst is expressed by the average diameter, which in the case of an ellipsoid or a nearly spherical shape or the like means the equivalent diameter. The average diameter of the spherical catalyst of the present invention is not particularly limited, but is preferably 4 to 10mm, more preferably 6 to 10 mm. The inventor finds that the heat conductivity of silicon is higher than that of silicon carbide, steel, iron, corundum and talc, and the silicon has lower hardness, so the silicon is most suitable for being used as a carrier of a catalyst, and by using silicon balls with excellent heat conductivity as the carrier of the catalyst, the heat generated in the catalytic reaction process can be taken away in time, so that the catalyst keeps high activity; in addition, the catalyst is made into a double-layer structure, the inner layer is a silicon ball impregnated with molybdenum oxide components, the outer layer is a coated Mo-Bi-Fe-Co-Ni composite oxide active component, and when the molybdenum components in the outer layer flow under the action of high-temperature water vapor in the reaction process, the molybdenum oxide in the inner layer can supplement the loss of the molybdenum in the outer layer, so that the catalyst keeps high activity and selectivity, and the service life is prolonged.
Therefore, the catalyst of the invention solves two problems of heat increase generated by reaction hot spots and loss of molybdenum components in the reaction process.
[ method for producing catalyst of the present invention ]
Preferred embodiments of the method for producing the catalyst of the present invention will be described below.
The catalyst for producing acrolein and/or acrylic acid of the present invention can be produced by the following steps.
Firstly, preparing silicon spheres, forming a molybdenum-containing coating on the surfaces of the silicon spheres, and then roasting in an oxygen-containing atmosphere to obtain the silicon spheres with the molybdenum oxide loading of 1-10 wt%.
In one embodiment of the present invention, when the molybdenum-containing coating layer is formed on the surface of the silicon spheres, the ammonium paramolybdate aqueous solution may be applied to the surface of the silicon spheres by dipping or spraying. In the case of firing, for example, firing may be performed at 300 to 550 ℃ in an air atmosphere.
In a preferred embodiment, the silicon spheres used have an average diameter of 3 to 7mm and a specific surface area of 5 to 10m2(ii) in terms of/g. The concentration of the ammonium molybdate aqueous solution is not particularly limited, and may be, for example, 5 to 10% by weight.
Next, an active ingredient powder having a composition represented by the following general formula (1) is prepared,
Mo12BiaFebCocNidXeYfOg(1)
wherein X is at least one selected from W, Sb, Zn, Cr, Mn, Sn, Si and Ce; y is at least one selected from Na, K, Rb, Cs, Mg, Ca and Ba; a. b, c, d, e, f represent the atomic number of Bi, Fe, Co, Ni, X and Y, respectively, wherein:
a＝0.1～2.0，
b＝0.1～5，
c＝1～20，
d＝1～20，
e＝0～3，
f＝0.01～1.0，
g is the number of oxygen atoms satisfying the valence of the oxide.
In the preparation of the active ingredient powder of the above composition, it is preferable to prepare a slurry containing the active ingredient by a coprecipitation method, dry the prepared slurry in an oven, grind and pulverize it, and perform pre-baking in a kiln.
In a preferred embodiment, the slurry obtained as described above is dried preferably at 100 to 200 ℃ for 12 to 24 hours, more preferably at 150 to 180 ℃ for 12 to 24 hours. In the pre-baking, the baking is preferably performed at 150 to 400 ℃ for 2 to 10 hours, more preferably at 200 to 300 ℃ for 5 to 10 hours.
Then, the obtained active component powder is mixed with a binder to prepare slurry, the slurry is coated on the surface of a silica sphere carrying molybdenum oxide, and then calcination is performed to obtain a catalyst having an active component content of 15 to 40 wt% with respect to the total weight of the catalyst.
The binder preferably contains at least one selected from the group consisting of polyvinyl alcohol, polyacrylamide, polyethylene glycol and silica sol.
In a preferred embodiment, the binder is polyacrylamide or silica sol.
When the binder is used, it is preferably prepared as an aqueous solution having a concentration of 0.2 to 30% by weight. The active ingredient powder and the binder aqueous solution are preferably mixed at a mass ratio of 5 to 10:1, particularly preferably 5: 1.
When coating the silicon spheres, for example, the slurry may be fed into a drum coater together with the prepared molybdenum oxide-supported silicon spheres to coat the silicon spheres.
After coating the silicon spheres, drying the silicon spheres at 100-120 ℃, and coating the silicon spheres for multiple times according to requirements to form an active component coating with specified content. Then roasting at 400-600 ℃ in an oxygen-containing atmosphere, preferably at 500 ℃ in an air atmosphere for 5-10 hours to obtain the catalyst with the active component content of 15-40 wt% relative to the total weight of the catalyst.
Hereinafter, a preferred example of the method for producing the catalyst for producing acrolein and/or acrylic acid of the present invention will be described.
Silicon spheres with the average diameter of 3-7 mm are immersed in 5-10 wt% ammonium molybdate aqueous solution, filtered and dried, and then roasted at 150-400 ℃ in an air atmosphere. And carrying out multiple times of impregnation under the condition that the molybdenum oxide loading amount of the final silicon spheres reaches 1-10 wt%.
Ammonium paramolybdate and potassium nitrate were dissolved in deionized water, and ammonium paratungstate and the like were dissolved as necessary to obtain a solution a. Dissolving cobalt nitrate, ferric nitrate, nickel nitrate, concentrated nitric acid and bismuth nitrate in deionized water, and dissolving chromium nitrate, cerium nitrate and the like according to needs to obtain a solution B.
The solution B was added dropwise to the solution a with vigorous stirring to obtain a slurry. And drying the slurry in an oven at 100-200 ℃, grinding and crushing, and calcining in a kiln at 150-400 ℃ to obtain active component powder.
The active ingredient powder and the aqueous binder solution are uniformly mixed in a mass ratio of, for example, 5:1 to prepare a slurry for spray coating. Finally, the silica spheres loaded with molybdenum oxide were placed in a drum coater for coating. And drying the coated catalyst at 100-120 ℃, and coating for multiple times. And finally, roasting the coated catalyst at 400-600 ℃ in an air atmosphere to obtain a finished catalyst.
According to the above production method of the present invention, a catalyst for producing acrolein and/or acrylic acid having high activity, high selectivity and long life can be simply produced.
The technical features and advantages of the present invention will be further described below with reference to examples, but it should be understood that the present invention is not limited to these examples.
Example 1
[ preparation of catalyst ]
The molybdenum oxide-loaded silicon spheres are prepared by the following method:
100g of silicon spheres (black, bulk density 1.45 g/cm) having an average diameter of 5mm were placed3) Immersing in 5 wt% ammonium molybdate water solution, filtering, drying, and calcining at 350 deg.C for 5 hr. The above steps were repeated so that the molybdenum oxide loading of the final silicon spheres was 5 wt%.
1560g of ammonium paramolybdate and 8g of potassium nitrate were dissolved in 5000m L of deionized water to give solution A. 1400g of cobalt nitrate, 480g of iron nitrate, 520g of nickel nitrate, 50m L of concentrated nitric acid and 550g of bismuth nitrate were dissolved in 1450m L of deionized water to give solution B.
The solution B was added dropwise to the solution a with vigorous stirring to obtain a slurry. The slurry was dried in an oven at 155 ℃ for 12 hours, ground and pulverized, and then calcined in a kiln at 200 ℃ for 5 hours to obtain an active ingredient powder.
The composition of the catalyst active component powder prepared by the above method was calculated according to the amount of the raw materials added, and as a result, Mo ═ 12, Bi ═ 1.54, Fe ═ 1.61, Co ═ 6.53, Ni ═ 2.43, and K ═ 0.11, in addition to O, that is, the catalyst had the following composition:
Mo12Bi1.54Fe1.61Co6.53Ni2.43K0.11Ox；
wherein x is the number of oxygen atoms satisfying the valence of the oxide.
And uniformly mixing the active component powder and 2.5 wt% of polyacrylamide aqueous solution according to the mass ratio of 5:1 to prepare the slurry for spraying. Finally, the silicon spheres loaded with 5 wt% of molybdenum oxide are put into a drum coating machine for coating, and the coated catalyst is dried at 120 ℃ and then repeatedly coated for a plurality of times. And finally, roasting the coated catalyst for 5 hours at 500 ℃ in an air atmosphere to obtain a finished catalyst. The content of the active phase of the finished catalyst was 23% by weight.
[ evaluation of catalyst Performance ]
The prepared catalyst is weighed to be 20m L and is loaded into a reactor at the propylene space velocity of 90h-1Then, a mixed gas containing 10% by volume of propylene, 73% by volume of air, and 17% by volume of water vapor was introduced, and the reaction was carried out at 340 ℃ under normal pressure for 500 hours.
The salt bath temperature and the hot spot temperature (bed temperature) in the reaction were measured, and the temperature difference Δ T therebetween was calculated. The catalytic reactor is placed in a salt bath, the temperature displayed by the salt bath represents the reaction temperature, and the reaction temperature is measured by adopting an armored thermocouple; the hot spot temperature is the temperature at the highest point of the catalyst bed temperature and is measured by an armored thermocouple in the catalytic reactor jacket.
The propylene oxidation reaction is a strongly exothermic reaction, heat is released intensively on the catalyst particles, and heat is removed mainly by the salt bath. The better the heat conductivity of the catalyst, the faster the reaction heat is conducted to the salt bath, and the lower the temperature of the catalyst hot spot, so the smaller the temperature difference Δ T between the reaction temperature and the hot spot temperature, the better the heat conductivity, and is beneficial to the improvement of the catalyst selectivity and the extension of the stability.
The composition of the catalyst, the reaction temperature and the hot spot temperature of the propylene catalytic reaction, and the value of Δ T are shown in table 1. In addition, the conversion, aldehyde yield and acid yield of the reaction were measured, and the results are listed in table 1.
In order to evaluate the molybdenum loss resistance of the catalyst, the catalyst was treated with water vapor at 500 ℃ for 240 hours or 480 hours and then introduced with a raw material gas to evaluate, and the reaction temperature, the hotspot temperature, Δ T, and the conversion rate, aldehyde yield, and acid yield of the reaction of propylene catalysis are shown in table 1.
Example 2
The catalyst was prepared and evaluated in the same manner as in example 1 except that the amount of the supported molybdenum oxide was 10.0% by weight.
The results of the catalytic reaction after 500 hours at 340 ℃ under normal pressure are shown in Table 1.
Example 3
The preparation and evaluation of the catalyst were carried out as in example 1, except that the content of the active component was 15.0% by weight.
The results of the catalytic reaction after 500 hours at 358 ℃ under normal pressure are shown in Table 1.
Example 4
The preparation and evaluation of the catalyst were carried out as in example 1, except that the active component content was 40.0% by weight.
The results of the catalytic reaction after 500 hours at atmospheric pressure and 328 ℃ are shown in Table 1.
Example 5
The catalyst was prepared and evaluated in the same manner as in example 1 except that the amount of molybdenum oxide supported on the silica spheres was 1% by weight.
The results of the catalytic reaction after 500 hours at 340 ℃ under normal pressure are shown in Table 1.
The molybdenum loss resistance of the catalyst was evaluated by treating the catalyst with steam at 500 ℃ for 240 hours and then introducing a raw material gas, and the results of the reaction at atmospheric pressure and 330 ℃ are also shown in Table 1.
Example 6
[ preparation of catalyst ]
The molybdenum oxide-loaded silicon spheres are prepared by the following method:
100g of silicon spheres having an average diameter of 5mm were immersed in a 5% by weight aqueous ammonium molybdate solution, filtered, dried and then calcined at 350 ℃ for 5 hours. And repeating the steps to ensure that the molybdenum oxide loading capacity of the final silicon spheres is 5 wt%.
1560g of ammonium paramolybdate and 8g of potassium nitrate were dissolved in 5000m L of deionized water to obtain solution A. 1400g of cobalt nitrate, 480g of iron nitrate, 520g of nickel nitrate, 30g of chromium nitrate, 50m L of concentrated nitric acid and 550g of bismuth nitrate were dissolved in 1450m L of deionized water to obtain solution B.
The solution B was added dropwise to the solution a with vigorous stirring to obtain a slurry. The slurry was dried in an oven at 155 ℃ for 12 hours, ground and pulverized, and then calcined in a kiln at 200 ℃ for 5 hours to obtain an active ingredient powder.
The composition of the catalyst active component powder prepared by the above method was calculated according to the amount of the raw materials added, and as a result, Mo ═ 12, Bi ═ 1.54, Fe ═ 1.61, Co ═ 6.53, Ni ═ 2.43, Cr ═ 0.71, and K ═ 0.11, except for O, that is, the catalyst had the following composition:
Mo12Bi1.54Fe1.61Co6.53Ni2.43Cr0.71K0.11Ox；
wherein x is the number of oxygen atoms satisfying the valence of the oxide.
And uniformly mixing the active component powder and 2.5 wt% of polyacrylamide aqueous solution according to the mass ratio of 5:1 to prepare the slurry for spraying. Finally, the silica spheres loaded with 5 wt% molybdenum oxide were placed in a drum coater for coating. And drying the coated catalyst at 120 ℃, and then coating for multiple times. And finally, roasting the coated catalyst for 5 hours at 500 ℃ in an air atmosphere to obtain a finished catalyst. The content of the active phase of the finished catalyst was 23% by weight.
[ catalyst evaluation ]
The prepared catalyst is weighed to be 20m L and is loaded into a reactor at the propylene space velocity of 90h-1Then, a mixed gas containing 10% by volume of propylene, 73% by volume of air, and 17% by volume of water vapor was introduced, and the reaction was carried out at 345 ℃ under normal pressure, and the results after 500 hours of the reaction were shown in Table 1.
Example 7
The catalyst was prepared as in example 6 except that the amount of chromium nitrate added was changed to 14.8 g. The active phase composition of the catalyst is, in addition to O, Mo ═ 12, Bi ═ 1.54, Fe ═ 1.61, Co ═ 6.53, Ni ═ 2.43, Cr ═ 0.35, and K ═ 0.11. Namely, the catalyst has the following composition:
Mo12Bi1.54Fe1.61Co6.53Ni2.43Cr0.35K0.11Ox；
wherein x is the number of oxygen atoms satisfying the valence of the oxide.
[ catalyst evaluation ]
The prepared catalyst is weighed to be 20m L and is loaded into a reactor at the propylene space velocity of 90h-1Then, a mixed gas containing 10% by volume of propylene, 73% by volume of air, and 17% by volume of water vapor was introduced, and the reaction was carried out at 353 ℃ under normal pressure, and the results after 500 hours of the reaction were shown in Table 1.
Example 8
The molybdenum oxide-loaded silicon spheres are prepared by the following method:
100g of silicon spheres having an average diameter of 5mm were immersed in a 5% by weight aqueous ammonium molybdate solution, filtered, dried and then calcined at 350 ℃ for 5 hours. And repeating the steps to ensure that the molybdenum oxide loading capacity of the final silicon spheres is 5 wt%.
1560g of ammonium paramolybdate 38.5g of ammonium paratungstate and 8g of potassium nitrate were dissolved in 5000m L of deionized water to obtain solution A. 1400g of cobalt nitrate, 480g of ferric nitrate, 520g of nickel nitrate, 50m L of concentrated nitric acid and 550g of bismuth nitrate were dissolved in 1450m L of deionized water to obtain solution B.
The solution B was added dropwise to the solution a with vigorous stirring to obtain a slurry. The slurry was dried in an oven at 155 ℃ for 12 hours, ground and pulverized, and then calcined in a kiln at 200 ℃ for 5 hours to obtain an active ingredient powder.
The composition of the catalyst active component powder prepared by the above method was calculated according to the amount of the raw materials added, and as a result, Mo ═ 12, Bi ═ 1.54, Fe ═ 1.61, Co ═ 6.53, Ni ═ 2.43, W ═ 0.20, and K ═ 0.11, except for O, that is, the catalyst had the following composition:
Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.20K0.11Ox；
wherein x is the number of oxygen atoms satisfying the valence of the oxide.
And uniformly mixing the active component powder and 2.5 wt% of polyacrylamide aqueous solution according to the mass ratio of 5:1 to prepare the slurry for spraying. Finally, the silica spheres loaded with 5 wt% molybdenum oxide were placed in a drum coater for coating. And drying the coated catalyst at 120 ℃, and then coating for multiple times. And finally, roasting the coated catalyst for 5 hours at 500 ℃ in an air atmosphere to obtain a finished catalyst. The content of the active phase of the finished catalyst was 23% by weight.
[ catalyst evaluation ]
The prepared catalyst is weighed to be 20m L and is loaded into a reactor at the propylene space velocity of 90h-1Then, a mixed gas containing 10% by volume of propylene, 73% by volume of air, and 17% by volume of water vapor was introduced, and the reaction was carried out at 340 ℃ under normal pressure, and the results after 500 hours of the reaction were shown in Table 1.
Example 9
The catalyst was prepared as in example 8 except that the amount of W was 57.75 g. The active phase composition of the catalyst is, in addition to O, Mo ═ 12, Bi ═ 1.54, Fe ═ 1.61, Co ═ 6.53, Ni ═ 2.43, W ═ 0.30, and K ═ 0.11. Namely, the catalyst has the following composition:
Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.30K0.11Ox；
wherein x is the number of oxygen atoms satisfying the valence of the oxide.
[ catalyst evaluation ]
The prepared catalyst is weighed to be 20m L and is loaded into a reactor at the propylene space velocity of 90h-1Then, a mixed gas containing 10% by volume of propylene, 73% by volume of air, and 17% by volume of water vapor was introduced, and the reaction was carried out at 335 ℃ under normal pressure, and the results after 500 hours of the reaction were shown in Table 1.
Example 10
The catalyst was prepared as in example 8 except that the amount of W was 77 g. The active phase composition of the catalyst is, in addition to O, Mo ═ 12, Bi ═ 1.54, Fe ═ 1.61, Co ═ 6.53, Ni ═ 2.43, W ═ 0.40, and K ═ 0.11. Namely, the catalyst has the following composition:
Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.40K0.11Ox；
wherein x is the number of oxygen atoms satisfying the valence of the oxide.
[ catalyst evaluation ]
The prepared catalyst is weighed to be 20m L and is loaded into a reactor at the propylene space velocity of 90h-1Then, a mixed gas containing 10% by volume of propylene, 73% by volume of air, and 17% by volume of water vapor was introduced, and the reaction was carried out at 340 ℃ under normal pressure, and the results after 500 hours of the reaction were shown in Table 1.
Example 11
The molybdenum oxide-loaded silicon spheres are prepared by the following method:
100g of silicon spheres having an average diameter of 5mm were immersed in a 5% by weight aqueous ammonium molybdate solution, filtered, dried and then calcined at 350 ℃ for 5 hours. And repeating the steps to ensure that the molybdenum oxide loading capacity of the final silicon spheres is 5 wt%.
1560g of ammonium paramolybdate, 38.5g of ammonium paratungstate and 8g of potassium nitrate were dissolved in 5000m L of deionized water to obtain solution A. 1400g of cobalt nitrate, 480g of iron nitrate, 520g of nickel nitrate, 43g of cerium nitrate, 50m L of concentrated nitric acid and 550g of bismuth nitrate were dissolved in 1450m L of deionized water to obtain solution B.
The solution B was added dropwise to the solution a with vigorous stirring to obtain a slurry. The slurry was dried in an oven at 155 ℃ for 12 hours, ground and pulverized, and then calcined in a kiln at 200 ℃ for 5 hours to obtain an active ingredient powder.
The composition of the catalyst active component powder prepared by the above method was calculated according to the amount of the raw materials added, and as a result, Mo ═ 12, Bi ═ 1.54, Fe ═ 1.61, Co ═ 6.53, Ni ═ 2.43, W ═ 0.20, Ce ═ 0.94, and K ═ 0.11, except for O, that is, the catalyst had the following composition:
Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.20Ce0.94K0.11Ox；
wherein x is the number of oxygen atoms satisfying the valence of the oxide.
And uniformly mixing the active component powder and 2.5 wt% of polyacrylamide aqueous solution according to the mass ratio of 5:1 to prepare the slurry for spraying. Finally, the silica spheres loaded with 5 wt% molybdenum oxide were placed in a drum coater for coating. And drying the coated catalyst at 120 ℃, and then coating for multiple times. And finally, roasting the coated catalyst for 5 hours at 500 ℃ in an air atmosphere to obtain a finished catalyst. The content of the active phase of the finished catalyst was 23% by weight.
[ catalyst evaluation ]
The prepared catalyst is weighed to be 20m L and is loaded into a reactor at the propylene space velocity of 90h-1Then, a mixed gas containing 10% by volume of propylene, 73% by volume of air, and 17% by volume of water vapor was introduced, and the reaction was carried out at 340 ℃ under normal pressure, and the results after 500 hours of the reaction were shown in Table 1.
Example 12
The catalyst was prepared as in example 11 except that the binder added during the formation was a 30% by weight silica sol. The catalyst has an active phase composition other than O, i.e., Mo ═ 12, Bi ═ 1.54, Fe ═ 1.61, Co ═ 6.53, Ni ═ 2.43, W ═ 0.20, Ce ═ 0.94, and K ═ 0.11, i.e., it has the following composition:
Mo12Bi1.54Fe1.61Co6.53Ni2.43W0.20Ce0.94K0.11Ox；
wherein x is the number of oxygen atoms satisfying the valence of the oxide.
[ catalyst evaluation ]
The prepared catalyst is weighed to be 20m L and is loaded into a reactor at the propylene space velocity of 90h-1Then, a mixed gas containing 10% by volume of propylene, 73% by volume of air, and 17% by volume of water vapor was introduced, and the reaction was carried out at 345 ℃ under normal pressure, and the results after 500 hours of the reaction were shown in Table 1.
Comparative example 1
The catalyst was prepared and evaluated in the same manner as in example 1 except that the amount of the supported molybdenum oxide was 0% by weight.
The results of the catalytic reaction after 500 hours at 340 ℃ under normal pressure are shown in Table 1.
The molybdenum loss resistance of the catalyst was evaluated by treating the catalyst with steam at 500 ℃ for 240 hours and then introducing a raw material gas, and the results of the reaction at atmospheric pressure and 325 ℃ are also shown in Table 1.
Comparative example 2
The preparation method and evaluation method of the catalyst were the same as in example 1 except that silicon carbide spheres were used instead of the silicon spheres.
The results of the catalytic reaction after 500 hours at 340 ℃ under normal pressure are shown in Table 1.
The evaluation of the molybdenum loss resistance of the catalyst was conducted by treating the catalyst with steam at 500 ℃ for 240 hours or 480 hours and then introducing a raw material gas, and the results of the reaction at atmospheric pressure and 345 ℃ are also shown in Table 1.
Comparative example 3
The preparation method and evaluation method of the catalyst were the same as in example 1 except that corundum spheres were used instead of silicon spheres.
The results of the catalytic reaction after 500 hours at 340 ℃ under normal pressure are shown in Table 1.
The evaluation of the molybdenum loss resistance of the catalyst was conducted by treating the catalyst with steam at 500 ℃ for 240 hours or 480 hours and then introducing a raw material gas, and the results of the reaction at atmospheric pressure and 345 ℃ are also shown in Table 1.
Comparative example 4
The preparation and evaluation of the catalyst were carried out as in example 1, except that the content of the active component was 10.0% by weight.
The results of the catalytic reaction after 500 hours at 365 ℃ under normal pressure are shown in Table 1.
As can be seen from Table 1, the catalyst of example 1 had good catalytic activity, Δ T of 56 ℃, and good heat conductivity. After 240 hours of steam treatment and 480 hours of steam treatment, the catalyst still has good catalytic activity and thermal conductivity, which shows that even if the molybdenum component on the surface layer of the catalyst is lost under the action of high-temperature steam, the molybdenum oxide coating on the inner layer can timely complement the molybdenum component, and the service life of the catalyst is long.
The catalysts of examples 2 to 12 also had good catalytic activity, Δ T was 60 ℃ or less, and thermal conductivity was good. In example 5, the molybdenum oxide loading was 1% by weight, and the catalytic activity was good even after 240 hours of steam treatment, and Δ T was 60 ℃.
In comparative example 1, the catalyst has no molybdenum oxide coating layer and exhibits good catalytic activity and thermal conductivity in propylene catalytic reaction, but after 240 hours of treatment with steam, the catalyst performance is drastically deteriorated with the loss of the molybdenum component, the aldehyde yield is decreased, and Δ T is more than 60 ℃.
In comparative examples 2 and 3, silicon carbide spheres and corundum spheres were used as carriers, respectively, and the catalytic activity of the catalyst in the propylene catalytic reaction was good, but the aldehyde yield was relatively low compared to examples 1 to 12, and in addition, Δ T was high, 65 ℃ in comparative example 2 and 72 ℃ in comparative example 3, and thus the thermal conductivity of the catalyst was poor. The catalysts of comparative examples 2 and 3 had low catalytic performance and poor thermal conductivity after 240 hours and 480 hours of steam treatment.
In comparative example 4, in which a catalyst having an active ingredient content of 10 wt% was used, it was found that outside the scope of the present invention, the reaction temperature was increased to 365 ℃ in the catalytic reaction to achieve the industrially required propylene conversion of > 98%, and the total yield of the desired aldehyde and acid was also reduced. It can be seen that when the active component content of the catalyst is below the range of the present invention, the overall performance of the catalyst is reduced.
Finally, it should be understood that the above description of the embodiments and examples is illustrative in all respects, not restrictive, and that various modifications may be made without departing from the spirit of the invention. The scope of the invention is indicated by the claims rather than by the foregoing description of embodiments or examples. The scope of the present invention includes all modifications within the meaning and range equivalent to the claims.
Industrial applicability of the invention
The catalyst of the present invention solves the problems of increase in heat generation due to hot spots and loss of the molybdenum component under the action of high-temperature steam in the oxidation reaction of propylene, has high activity, selectivity and long life, is suitable for use as a catalyst for the production of acrolein and/or acrylic acid, and is therefore industrially useful.
Claims (10)
1. A catalyst for producing acrolein and/or acrylic acid, which is a catalyst having a silica sphere as a carrier and having an inner and outer double-layered coating, the inner layer comprising molybdenum oxide and the outer layer comprising a Mo-Bi-Fe-Co-Ni composite oxide active component having a general formula represented by the following formula (1):
Mo12BiaFebCocNidXeYfOg(1)
wherein X is at least one selected from W, Sb, Zn, Cr, Mn, Sn, Si and Ce; y is at least one selected from Na, K, Rb, Cs, Mg, Ca and Ba;
a. b, c, d, e, f represent the atomic number of Bi, Fe, Co, Ni, X and Y, respectively, wherein:
a＝0.1～2.0，
b＝0.1～5，
c＝1～20，
d＝1～20，
e＝0～3，
f＝0.01～1.0，
g is the number of oxygen atoms satisfying the valence of the oxide.
2. The catalyst of claim 1, wherein the silica spheres have an average diameter of 3 to 7 mm.
3. The catalyst according to claim 1, wherein the silica spheres have a specific surface area of 5 to 10m2/g。
4. The catalyst of claim 1 or 2, wherein the catalyst has an average diameter of 4 to 10 mm.
5. The catalyst according to claim 1, wherein the molybdenum oxide in the molybdenum oxide coating layer is supported at 1 to 10 wt% with respect to the silicon spheres.
6. The catalyst according to claim 1, wherein the active component is contained in an amount of 15 to 40 wt% with respect to the catalyst.
7. A method for producing the catalyst according to any one of claims 1 to 6, comprising the steps of:
1) providing silicon spheres, forming a molybdenum-containing coating on the surfaces of the silicon spheres, and then roasting in an oxygen-containing atmosphere to obtain the silicon spheres with the molybdenum oxide loading amount of 1-10 wt%;
2) preparing an active ingredient powder having a composition represented by the following general formula (1),
Mo12BiaFebCocNidXeYfOg(1)
wherein X is at least one selected from W, Sb, Zn, Cr, Mn, Sn, Si and Ce; y is at least one selected from Na, K, Rb, Cs, Mg, Ca and Ba; a. b, c, d, e, f represent the atomic number of Bi, Fe, Co, Ni, X and Y, respectively, wherein:
a＝0.1～2.0，
b＝0.1～5，
c＝1～20，
d＝1～20，
e＝0～3，
f＝0.01～1.0，
g is the number of oxygen atoms satisfying the valence state of the oxide;
3) preparing the obtained active component powder into slurry, arranging the slurry on the surface of a silicon sphere carrying molybdenum oxide, and then roasting to obtain the catalyst with the active component content of 15-40 wt% relative to the total weight of the catalyst.
8. The method for producing the catalyst according to claim 7, wherein the silica spheres have an average diameter of 3 to 7mm and a specific surface area of 5 to 10m2/g。
9. The method for producing a catalyst according to claim 7, wherein the slurry is obtained by mixing the active component powder with a binder, and the binder is at least one selected from the group consisting of polyvinyl alcohol, polyacrylamide, polyethylene glycol, and silica sol.
10. The method for producing the catalyst according to claim 9, wherein the binder is prepared in an aqueous solution having a concentration of 0.2 to 30% by weight, and the active component powder and the aqueous binder solution are mixed in a mass ratio of 5:1 to 10: 1.
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