CN110743558A - Preparation method and application of eggshell type composite metal catalyst - Google Patents
Preparation method and application of eggshell type composite metal catalyst Download PDFInfo
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- CN110743558A CN110743558A CN201911241585.5A CN201911241585A CN110743558A CN 110743558 A CN110743558 A CN 110743558A CN 201911241585 A CN201911241585 A CN 201911241585A CN 110743558 A CN110743558 A CN 110743558A
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 28
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 28
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000002808 molecular sieve Substances 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000008262 pumice Substances 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000008279 sol Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052875 vesuvianite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910006587 β-Al2O3 Inorganic materials 0.000 claims description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 2
- 238000001175 rotational moulding Methods 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract 1
- 239000000463 material Substances 0.000 description 37
- 238000003756 stirring Methods 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 16
- 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
- 239000007787 solid Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 10
- 239000000126 substance 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 8
- 239000011609 ammonium molybdate Substances 0.000 description 8
- 229940010552 ammonium molybdate Drugs 0.000 description 8
- 235000018660 ammonium molybdate Nutrition 0.000 description 8
- 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
- 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
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 description 1
- BSKSXTBYXTZWFI-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;acetate Chemical compound CC([O-])=O.CCCC[N+]=1C=CN(C)C=1 BSKSXTBYXTZWFI-UHFFFAOYSA-M 0.000 description 1
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- PXJUBOLFJDSAQQ-UHFFFAOYSA-M tetrapropylazanium;acetate Chemical compound CC([O-])=O.CCC[N+](CCC)(CCC)CCC PXJUBOLFJDSAQQ-UHFFFAOYSA-M 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011701 zinc 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
- 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
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an eggshell type composite metal oxide catalyst for synthesizing methacrolein by gas phase oxidation of isobutene/tertiary butanol. Adding a spherical carrier and a binder in the preparation process of the catalyst to enable metal salt to react on the surface of the spherical carrier and attach to the surface of the spherical carrier, and removing part of the binder through roasting to obtain the eggshell type composite metal oxide catalyst. The catalyst provided by the invention has the advantages of simple preparation process, low cost, excellent catalytic performance in the reaction of synthesizing methacrolein by isobutene/tert-butyl alcohol gas phase oxidation, long catalytic life and suitability for industrialization.
Description
Technical Field
The invention relates to a preparation method of an eggshell type composite metal oxide catalyst and application of the eggshell type composite metal oxide catalyst in a reaction of synthesizing methacrolein by isobutene/tertiary butanol gas phase oxidation, belonging to the field of catalyst preparation and application.
Background
As an important organic chemical raw material and an industrial intermediate, Methyl Methacrylate (MMA) is mainly used for producing organic glass (PMMA), a light guide plate, a light guide fiber and the like, and because PMMA has excellent physical and chemical properties, the PMMA has important application in national important industries such as LED, aviation, rail transit and the like. The acetone cyanohydrin method is a traditional production process of MMA, and because virulent hydrocyanic acid and strong corrosive sulfuric acid are used in the production process and the environment is seriously polluted, a new alternative process meeting the green chemical requirement is urgently needed.
At present, the new process meeting the green chemical requirements in the development stage mainly focuses on a C4 clean production process, and can be divided into a two-step method and a three-step method according to different reaction steps, wherein the two-step method mainly comprises the steps of synthesizing methacrolein through isobutene/tertiary butanol oxidation and synthesizing methyl methacrylate, namely MMA through one-step oxidation esterification; the three-step method mainly comprises the steps of synthesizing methacrolein by oxidizing isobutene/tertiary butanol, oxidizing methacrolein to generate methacrylic acid and esterifying the methacrylic acid to obtain MMA. The two processes belong to green processes, the process is simple, the operation cost is low, and as key reaction steps of the two processes, the catalyst for synthesizing methacrolein by oxidizing isobutene/tert-butanol is mainly based on Mo-Bi-Fe-Co-O composite oxide, trace elements are added into the basic components to achieve relatively high catalyst activity, but the catalysts have two more difficult problems in the industrial application process: 1. the strong heat release causes the performance reduction and the service life reduction of the catalyst; 2. the reaction of isobutene is incomplete to affect the activity of the catalyst for the subsequent reaction.
To solve the first problem, patents US5728894 and US7012039 disclose a method for achieving the purpose of prolonging the life of a catalyst by suppressing the loss of Mo as an active component by adding a component having heat resistance and reduction resistance, but this cannot fundamentally solve the problem; on the basis, the patents CN1210511A, CN145946A and CN1048540A respectively improve the thermal conductivity of the catalyst by loading and adding inert substances to dilute the catalyst, thereby inhibiting the Mo component from losing due to high temperature in the reaction process, but these methods not only reduce the activity and product yield of the catalyst more or less, but also make the preparation process and the filling process of the catalyst more complicated.
The second problem is focused on the three-step process, in which the catalyst for the preparation of methacrylic acid by oxidation of methacrolein is very sensitive to isobutylene, and excessive residual isobutylene causes poisoning deactivation of the catalyst, and therefore, in order to improve the economy of the production process and the catalyst life of the subsequent reaction, it is necessary to react isobutylene in the first step as completely as possible. Japanese patent laid-open No. Sho 55(1980) -113730 improves the activity and selectivity of the catalyst by changing the addition of K, Rb, Cs, Ti and other elements. In the methods disclosed in chinese patents CN103157486A and CN1647853A, the method of preparing the catalyst in a supported manner is adopted to improve the distribution of active components of the catalyst, thereby improving the activity of the catalyst. Despite the modest advances in conversion, the requirements for the production of methacrylic acid catalysts by the oxidation of methacrolein are still not met and a reduction in methacrolein selectivity results.
According to the requirements of the existing production process, a new preparation method of the catalyst needs to be developed, and the eggshell type composite metal oxide catalyst with high activity and strong thermal stability is prepared.
Disclosure of Invention
The invention provides a preparation method of an eggshell type composite metal oxide catalyst with excellent catalytic performance, high thermal stability, simple method and low cost. In the invention, the spherical carrier and the binder are added in the preparation process of the catalyst, so that the metal salt reacts on the surface of the spherical carrier and is attached to the surface of the spherical carrier, and then part of the binder is removed by roasting, thereby obtaining the eggshell type composite metal oxide catalyst. The catalyst is used for the reaction of synthesizing methacrolein by isobutene/tertiary butanol gas phase oxidation, and shows excellent catalytic performance and service life.
The chemical expression of the eggshell type composite metal oxide catalyst is as follows:
Mo12BiaFebCocXdYeOm/Z
wherein,
x is one or more selected from Cu, Mg, Ni, V, Ti and Zn;
y is one or more selected from K, Na, Cs, La, Ce, Nd, Zr, Nb, Yb, Er, Sb, Sr and Ag;
z is a spherical carrier selected from porous silica gel, α -Al2O3、β-Al2O3、γ-Al2O3One or more of silicon-aluminum molecular sieves such as MCM-41 molecular sieve, KIT-6 molecular sieve, SBA-15 and the like;
a. b, c, d, e, m represent the atomic ratio of each element in one catalyst cluster, respectively, wherein,
the range of a is selected from 0.1-6;
b is selected from 0.1-6;
c is selected from 0.5-10;
d is selected from 0.05-4;
e is selected from 0.05-3;
m is the number of oxygen atoms satisfying the oxidation state of the above elements.
The preparation process of the catalyst comprises the following steps:
a) under certain conditions, a certain amount of binder and a certain proportion of metal salt aqueous solution are fully mixed and dissolved;
b) mixing the solution prepared in the step with a precipitator and a spherical carrier under a certain condition, reacting, aging and refluxing to form suspension slurry;
c) and (3) drying and roasting the suspension slurry prepared in the step under a certain condition to obtain the eggshell type composite metal oxide catalyst.
d) And (3) molding the catalyst powder prepared in the step under a certain condition to obtain the regular or irregular catalyst to be evaluated.
The binder in the step a) is selected from one or more of silica sol, aluminum sol, titanium sol, bentonite, ethylene glycol, polyethylene oxide, polytetrafluoroethylene, polyvinylpyrrolidone, ionic liquid binder and the like, and the titanium sol, the polyethylene glycol, the polytetrafluoroethylene, the polyvinylpyrrolidone and the ionic liquid are preferred; the mass ratio of the binder to the metal salt is 1: 100-1: 5, preferably 1: 80-1: 20; the dissolution temperature is 20-80 ℃.
The spherical carrier in the step b) is selected from one or more of silica-alumina molecular sieves such as silica, alumina, MCM-41 molecular sieve, KIT-6 molecular sieve and SBA-15, magnesia, zirconia, aluminum silicate, diatomite, pumice, vesuvianite and kaolin, preferably silica, alumina, MCM-41 molecular sieve, SBA-15, magnesia and zirconia, and the diameter of the spherical carrier is 1-300 mu m, preferably 10-100 mu m; the spherical carrier can be mixed with a precipitant or the solution prepared in the step a), or the precipitant and the metal salt solution containing the binder can be jointly dripped into the suspension water solution of the spherical carrier; the mass ratio of the spherical carrier to the metal salt is 20: 1-0.5: 1; the reaction temperature is 30-100 ℃, the aging reflux temperature is 50-150 ℃, and the time is 1-12 h.
The drying mode in the step c) can be one of evaporation drying, vacuum drying, microwave drying, suction filtration drying, spray drying or reduced pressure rotary evaporation drying; the roasting temperature is 350-650 ℃, preferably 400-500 ℃, the heating rate is 1-10 ℃/min, preferably 3-6 ℃/min, and the roasting time is 2-24 h, preferably 4-10 h.
The forming mode in the step d) is one selected from tabletting forming, extrusion molding, rotation forming, spray forming, roll coating forming and dipping forming.
The eggshell type composite metal oxide catalyst prepared by the invention is used for catalyzing isobutene gas phase oxidation in a gas phase to synthesize methacrolein in a fixed bed through molecular oxygen in air.
The isobutene conversion was calculated as follows:
x (isobutylene)%, [1- (amount of unreacted isobutylene substance/amount of supplied isobutylene substance) ] × 100%
The selectivity of methacrolein is calculated as follows:
s (methacrolein)%, [ amount of substance of formed methacrolein/(amount of substance of supplied isobutylene-amount of unreacted isobutylene) ] × 100%
According to the invention, the binder and the spherical carrier are added in the preparation process of the catalyst, so that the metal salt and the precipitator directly react on the surface of the spherical carrier, and the addition of the binder and the rich groups on the surface of the spherical carrier enable the catalyst to be attached to the surface of the carrier under the action of the physical properties of the binder and the chemical bonds on the surface of the carrier to form an eggshell type structure, so that the temperature runaway of the catalyst can be effectively inhibited, and the inactivation caused by the loss of active components can be avoided to the greatest extent. Meanwhile, in the roasting process of the catalyst, a porous structure is formed due to the removal of part of the binder, so that the performance of the catalyst is effectively improved. The catalyst is used for synthesizing methacrolein by gas phase oxidation of isobutene, and has good catalytic performance and long catalytic life. The eggshell type catalyst has simple preparation process, and the used binder and carrier raw materials have low price and are suitable for industrial application.
Detailed Description
The present invention is illustrated below by way of examples, but the scope of the present invention is not limited by the examples.
Example 1
Weighing 5g of titanium sol, 40g of bismuth nitrate, 14g of copper nitrate, 63g of ferric nitrate, 131g of cobalt nitrate, 18g of cesium nitrate and 4g of lanthanum nitrate, and stirring and dissolving in 200ml of deionized water at the temperature of 30 ℃ to obtain a material A; weighing 200ml of deionized water, and adding 300g of SBA-15 molecular sieve with the particle size range of 20-60 mu m and 300g of ammonium molybdate to obtain a material B; and slowly adding the material A into the material B placed in a water bath at 55 ℃ under rapid stirring to form slurry, and stirring, aging and refluxing for 8 hours at 70 ℃ to obtain the required catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 75 ℃ to dryness, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 400 ℃ for 6 hours to roast to obtain eggshell type composite metal oxide catalyst powder.
Tabletting the catalyst powder, and pulverizing to 40-80 mesh.
2.0 ml of the obtained 40-80 mesh eggshell type composite metal oxide catalyst is mixed with quartz sand with equal particle size according to the volume ratio of 1:1 and is filled in a fixed bed reactor with the inner diameter of 10mm, the upper part and the lower part of the catalyst are filled with the quartz sand with equal particle size, and the mixture is prepared by mixing the following components in percentage by weight: oxygen: the mixed gas of nitrogen gas 1:1.9:11.5 (mol ratio) is used as raw material, and the space velocity is 1600h-1Reacting at 365 ℃ under normal pressure, and continuously reacting for 20 hours, and then carrying out gas chromatography on-line analysis.
It was found that the conversion of isobutylene was 97.7% and the selectivity of MAL was 80.9%.
Example 2
Weighing 8g of polyethylene glycol, 60g of bismuth nitrate, 20g of copper nitrate, 72g of ferric nitrate, 148g of cobalt nitrate, 28g of cesium nitrate and 8g of cerium nitrate, and stirring and dissolving in 300ml of deionized water at 40 ℃ to obtain a material A; measuring 300ml of deionized water, and adding 350g of ammonium molybdate to obtain a material B; weighing 200ml of deionized water, and adding 150g of gamma-Al with the particle size range of 50-90 mu m2O3Obtaining a material C; the materials A and B were slowly added to material C in a 50 ℃ water bath with rapid stirring to form a slurry, and aged at 80 ℃ under reflux for 12 hours to give the desired catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 90 ℃ to dryness, crushing the obtained solid, placing the crushed solid in an air atmosphere at 450 ℃ for 6 hours, and roasting to obtain eggshell type composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutylene was 97.5% and the selectivity of MAL was 79.6%.
Example 3
Weighing 4g of 1-butyl-3-methylimidazole acetate, 35g of bismuth nitrate, 152g of cobalt nitrate, 6g of potassium nitrate, 51g of ferric nitrate, 4g of cesium nitrate and 4g of cerium nitrate, and stirring and dissolving in 200ml of deionized water at the temperature of 30 ℃ to obtain a material A; measuring 200ml of deionized water, and adding 200g of ammonium molybdate to obtain a material B; weighing 150ml of deionized water, and adding 150g of MCM-41 molecular sieve with the particle size range of 20-70 mu m to obtain a material C; the materials A and B were slowly added to material C in a 50 ℃ water bath with rapid stirring to form a slurry, and the slurry was aged under stirring at 100 ℃ for 10 hours under reflux to give the desired catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 80 ℃, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 450 ℃ for 8 hours to roast to obtain eggshell type composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 98.4% and the selectivity of MAL was 81.8%.
Example 4
Weighing 10g of tetrapropyl ammonium acetate, 52g of bismuth nitrate, 182g of cobalt nitrate, 10g of sodium nitrate, 56g of ferric nitrate, 4g of cesium nitrate and 12g of copper nitrate, and stirring and dissolving the materials in 300ml of deionized water at 45 ℃ to obtain a material A; weighing 300ml of deionized water, and adding 260g of ammonium molybdate and 150g of MCM-41 molecular sieve with the particle size range of 20-70 mu m to obtain a material B; and slowly adding the material A into the material B placed in a water bath at 50 ℃ under rapid stirring to form slurry, and stirring, aging and refluxing for 7 hours at 120 ℃ to obtain the required catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 90 ℃ to dryness, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 500 ℃ for 6 hours to roast to obtain eggshell type composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutylene was 99.6% and the selectivity of MAL was 84.2%.
After the continuous operation for 1000 hours, the conversion rate of isobutene is kept above 99.0%, and the selectivity of MAL is kept above 82.0%.
Example 5
Weighing 10g of polyvinylpyrrolidone, 48g of bismuth nitrate, 212g of cobalt nitrate, 20g of zinc nitrate, 65g of ferric nitrate, 6g of cesium nitrate and 19g of cerium nitrate, and stirring and dissolving in 300ml of deionized water at the temperature of 30 ℃ to obtain a material A; weighing 400ml of deionized water, and adding 300g of ammonium molybdate and 300g of HZSM-5 molecular sieve with the particle size range of 40-60 mu m to obtain a material B; and slowly adding the material A into the material B placed in a water bath at 50 ℃ under rapid stirring to form slurry, and stirring, aging and refluxing for 9 hours at 100 ℃ to obtain the required catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 80 ℃, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 450 ℃ for 6 hours to roast to obtain eggshell type composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutylene was 97.2% and the selectivity of MAL was 83.3%.
Comparative example 1
Weighing 40g of bismuth nitrate, 14g of copper nitrate, 63g of ferric nitrate, 131g of cobalt nitrate, 18g of cesium nitrate and 4g of lanthanum nitrate, and stirring and dissolving in 200ml of deionized water at the temperature of 30 ℃ to obtain a material A; measuring 200ml of deionized water, and adding 300g of SBA-15 with the particle size range of 20-60 mu m and 300g of ammonium molybdate to obtain a material B; and slowly adding the material A into the material B placed in a water bath at 55 ℃ under rapid stirring to form slurry, and stirring, aging and refluxing for 8 hours at 70 ℃ to obtain the required catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 75 ℃ to dryness, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 400 ℃ for 6 hours to roast to obtain eggshell type composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutylene was 92.9% and the selectivity of MAL was 81.1%.
Comparative example 2
Except that the polyethylene glycol in example 2 was changed to undecyltrimethylammonium acetate, the catalyst powder was prepared by the method of example 2 to obtain eggshell-type composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutylene was 99.7% and the selectivity of MAL was 86.4%.
After the continuous operation for 1000 hours, the conversion rate of isobutene is kept above 99.0%, and the selectivity of MAL is kept above 86.0%.
Comparative example 3
An eggshell-type composite metal oxide catalyst powder was prepared by the method of example 3, except that 8g of silica sol was used instead of 1-butyl-3-methylimidazolium acetate in example 3.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutylene was 94.8% and the selectivity for MAL was 77.9%.
Comparative example 4
Except that the 150g MCM-41 molecular sieve in the example 4 is changed into 180g porous silica gel with the particle size range of 30-80 μm, the eggshell type composite metal oxide catalyst powder is prepared according to the method in the example 3.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutylene was 97.8% and the selectivity of MAL was 81.9%.
Comparative example 5
Weighing 10g of polyvinylpyrrolidone, 48g of bismuth nitrate, 212g of cobalt nitrate, 20g of zinc nitrate, 65g of ferric nitrate, 6g of cesium nitrate and 19g of cerium nitrate, and stirring and dissolving in 300ml of deionized water at the temperature of 30 ℃ to obtain a material A; measuring 200ml of deionized water, and adding 300g of ammonium molybdate to obtain a material B; weighing 200ml of deionized water, and adding 300g of HZSM-5 molecular sieve with the particle size range of 40-60 mu m to obtain a material C; and slowly adding the material A and the material B into the material C placed in a water bath at 50 ℃ under the condition of rapid stirring to form slurry, and stirring, aging and refluxing for 9 hours at 100 ℃ to obtain the required catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 80 ℃, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 450 ℃ for 6 hours to roast to obtain eggshell type composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutylene was 99.2% and the selectivity of MAL was 84.9%.
Comparative example 6
Weighing 52g of bismuth nitrate, 182g of cobalt nitrate, 10g of sodium nitrate, 56g of ferric nitrate, 4g of cesium nitrate and 12g of copper nitrate, and stirring and dissolving in 300ml of deionized water at 45 ℃ to obtain a material A; weighing 300ml of deionized water, and adding 260g of ammonium molybdate to obtain a material B; and slowly adding the material A into the material B placed in a water bath at 50 ℃ under rapid stirring to form slurry, and stirring, aging and refluxing for 7 hours at 120 ℃ to obtain the required catalyst slurry.
Stirring and evaporating the obtained catalyst slurry at 90 ℃ to dryness, crushing the obtained solid, and then placing the crushed solid in an air atmosphere at 500 ℃ for 6 hours to roast to obtain the composite metal oxide catalyst powder.
The catalyst was molded and evaluated as in example 1.
It was found that the conversion of isobutene was 98.3% and the selectivity of MAL was 81.6%.
After 1000h of continuous operation, the conversion of isobutene was 93.6% and the selectivity of MAL was 77.2%.
Claims (8)
1. The eggshell type composite metal oxide catalyst is characterized in that a spherical carrier and a binder are added in the preparation process of the catalyst, and metal salt directly reacts on the surface of the carrier and is attached to the surface of the carrier, so that the eggshell type composite metal oxide catalyst with high activity, good stability and low cost is obtained.
2. The eggshell composite metal oxide catalyst of claim 1 wherein said catalyst composition is:
Mo12BiaFebCocXdYeOm/Z
wherein,
x is one or more selected from Cu, Mg, Ni, V, Ti and Zn;
y is one or more selected from K, Na, Cs, La, Ce, Nd, Zr, Nb, Yb, Er, Sb, Sr and Ag;
z is a spherical carrier selected from porous silica gel, α -Al2O3、β-Al2O3、γ-Al2O3One or more of silicon-aluminum molecular sieves such as MCM-41 molecular sieve, KIT-6 molecular sieve, SBA-15 and the like;
a. b, c, d, e, m represent the atomic ratio of each element in one catalyst cluster, respectively, wherein,
the range of a is selected from 0.1-6;
b is selected from 0.1-6;
c is selected from 0.5-10;
d is selected from 0.05-4;
e is selected from 0.05-3;
m is the number of oxygen atoms satisfying the oxidation state of the above elements.
3. The method for preparing the eggshell type composite metal oxide catalyst as recited in claim 1 comprises the steps of:
a) under certain conditions, a certain amount of binder and a certain proportion of metal salt aqueous solution are fully mixed and dissolved;
b) mixing the solution prepared in the step with a precipitator and a spherical carrier under a certain condition, reacting, aging and refluxing to form suspension slurry;
c) drying and roasting the suspension slurry prepared in the step under a certain condition to obtain eggshell type composite metal oxide catalyst powder;
d) and (3) molding the catalyst powder prepared in the step under a certain condition to obtain the regular or irregular catalyst to be evaluated.
4. The method according to claim 3, wherein the binder in the step a) is one or more selected from silica sol, aluminum sol, titanium sol, bentonite, ethylene glycol, polyethylene oxide, polytetrafluoroethylene, polyvinylpyrrolidone, ionic liquid binder and the like, and the mass ratio of the binder to the metal salt is 1: 100-1: 5; the dissolution temperature is 20-80 ℃.
5. The method according to claim 3, wherein the spherical carrier in the step b) is selected from one or more of silica, alumina, MCM-41 molecular sieve, KIT-6 molecular sieve, silica-alumina molecular sieve such as SBA-15, magnesia, zirconia, aluminum silicate, diatomite, pumice, vesuvianite and kaolin, and the diameter of the spherical carrier is 1-300 μm; the spherical carrier can be mixed with the precipitant or the solution prepared in the step a) in advance, or the precipitant and the metal salt solution containing the binder can be dripped into the suspension water solution of the spherical carrier together; the mass ratio of the spherical carrier to the metal salt is 20: 1-0.5: 1; the reaction temperature is 30-100 ℃, the aging reflux temperature is 50-150 ℃, and the time is 1-12 h.
6. The method according to claim 3, wherein the drying in step c) is selected from one of evaporation drying, vacuum drying, microwave drying, suction filtration drying, spray drying or reduced pressure rotary evaporation drying; the roasting temperature is 350-650 ℃, the heating rate is 1-10 ℃/min, and the roasting time is 2-24 h.
7. The method according to claim 3, wherein the molding in the step d) is one selected from the group consisting of tablet molding, extrusion molding, rotational molding, spray molding, roll coating molding and dip molding.
8. A method for synthesizing methacrolein by gas phase oxidation of isobutylene/tert-butanol, characterized in that the eggshell-type composite metal oxide catalyst according to any one of claims 1 to 7 is used.
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| CN111203229A (en) * | 2020-02-19 | 2020-05-29 | 中国科学院过程工程研究所 | Preparation method and application of supported composite oxide catalyst |
| CN113828346A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Catalyst for preparing methacrolein and preparation method and application thereof |
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| CN111992248B (en) * | 2019-11-15 | 2021-07-23 | 北京水木滨华科技有限公司 | Catalyst for oxidation esterification of isobutene, preparation method and application thereof |
| CN112871182B (en) * | 2019-11-29 | 2022-04-12 | 中国科学院大连化学物理研究所 | Catalyst for preparing methylacrolein by oxidizing isobutene, preparation and application thereof |
| CN114425355B (en) * | 2020-09-27 | 2023-08-15 | 中国石油化工股份有限公司 | Catalyst for preparing methacrolein by fixed bed, preparation method and application |
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