CN114471556B - Hydrogen peroxide decomposition catalyst and preparation method and application thereof - Google Patents
Hydrogen peroxide decomposition catalyst and preparation method and application thereof Download PDFInfo
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- CN114471556B CN114471556B CN202011157838.3A CN202011157838A CN114471556B CN 114471556 B CN114471556 B CN 114471556B CN 202011157838 A CN202011157838 A CN 202011157838A CN 114471556 B CN114471556 B CN 114471556B
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- hydrogen peroxide
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- peroxide decomposition
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 259
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 186
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 65
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 65
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229920002472 Starch Polymers 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 239000008107 starch Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 8
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002674 ointment Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 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
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000003361 porogen Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 102100039111 FAD-linked sulfhydryl oxidase ALR Human genes 0.000 description 51
- 101000959079 Homo sapiens FAD-linked sulfhydryl oxidase ALR Proteins 0.000 description 34
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 241000219782 Sesbania Species 0.000 description 12
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- 238000006735 epoxidation reaction Methods 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- YROGWJLGNLJNOK-UHFFFAOYSA-N 1-chloro-1-methoxypropane Chemical compound CCC(Cl)OC YROGWJLGNLJNOK-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical compound CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910003438 thallium oxide Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229920000034 Plastomer Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J23/72—Copper
-
- 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
-
- B01J35/30—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a hydrogen peroxide decomposition catalyst, a preparation method and application thereof, wherein the hydrogen peroxide decomposition catalyst contains 21-39 wt% of IVB metal oxide, 21-40 wt% of IB metal oxide and 21-58 wt% of IIIA metal oxide. The hydrogen peroxide decomposition catalyst has higher side pressure crushing strength, and can efficiently decompose hydrogen peroxide in methanol aqueous solution.
Description
Technical Field
The invention relates to a hydrogen peroxide decomposition catalyst, a preparation method and application thereof.
Background
The epoxy chloropropane is an important basic organic chemical raw material and an intermediate, and is widely applied to various industrial products such as synthetic epoxy resin, chlorohydrin rubber, medicines, pesticides, surfactants, plasticizers and the like.
As disclosed in CN101747297A, continuous and stable synthesis of epichlorohydrin is realized for a long time under the condition that the conversion rate of hydrogen peroxide is higher than 97% and the selectivity of epichlorohydrin is higher than 95% by epoxidation reaction of 3-chloropropene and hydrogen peroxide in the presence of a titanium-silicon molecular sieve catalyst and a solvent methanol. However, the conversion of hydrogen peroxide is typically maintained between 97% and 99% during long run times such that the epoxidation reaction product contains 0.05% to 0.5% by mass hydrogen peroxide.
CN106140186a discloses a hydrogen peroxide decomposition catalyst and a method for decomposing hydrogen peroxide in a reaction product of 3-chloropropene and hydrogen peroxide epoxidation, wherein the catalyst contains 1 to 20 mass% of group ivb metal oxide, 1 to 20 mass% of group vib metal oxide, 1 to 20 mass% of group ib metal oxide and 40 to 97 mass% of group iiia metal oxide, and the decomposition of hydrogen peroxide in the reaction product of epoxidation is carried out at a temperature of 0 to 50 ℃ and a pressure of 0.1 to 2.0MPa, so that the decomposition of hydrogen peroxide in the reaction product of epoxidation can be reduced to below 0.02 mass%. However, this patent does not disclose the side crushing strength of the catalyst. The research shows that the lateral pressure crushing strength of the catalyst prepared by adopting the method disclosed in CN106140186A is obviously lower than 70N/cm, the catalyst is easy to crush, and the strength requirement of an industrial fixed bed reactor on the packed catalyst is difficult to meet.
Disclosure of Invention
The invention aims to provide a hydrogen peroxide decomposition catalyst, a preparation method and application thereof, and the catalyst can effectively decompose hydrogen peroxide and has higher strength.
The first aspect of the present invention provides a hydrogen peroxide decomposition catalyst comprising 21 to 39 wt% of a group IVB metal oxide, 21 to 40 wt% of a group IB metal oxide and 21 to 58 wt% of a group IIIA metal oxide.
Alternatively, the lateral pressure crushing strength of the hydrogen peroxide decomposition catalyst is 70 to 150N/cm, preferably 70 to 120N/cm.
Optionally, the hydrogen peroxide decomposition catalyst comprises 24 to 36 wt% group IVB metal oxide, 24 to 36 wt% group IB metal oxide and 28 to 52 wt% group IIIA metal oxide.
Optionally, the group IVB metal in the group IVB metal oxide includes one or more of titanium, zirconium and hafnium;
the IB metal in the IB metal oxide comprises one or more of copper, silver and gold;
the group IIIA metal in the group IIIA metal oxide comprises one or more of aluminum, gallium, indium and thallium.
Optionally, the group IVB metal oxide includes one or more of titanium dioxide, zirconium oxide and hafnium oxide, preferably titanium dioxide;
the IB group metal oxide is copper oxide;
the group IIIA metal oxide comprises one or more of aluminum oxide, gallium oxide, indium oxide and thallium oxide, preferably aluminum oxide.
In a second aspect, the present invention provides a process for preparing the hydrogen peroxide decomposition catalyst provided in the first aspect of the present invention, the process comprising:
(1) Mixing a IIIA metal source, a IVB metal oxide, a IB metal oxide, a binder and an auxiliary agent to obtain a mixture; the IIIA metal source is IIIA metal source hydroxide and/or IIIA metal oxide;
(2) The mixture is dried and calcined.
Optionally, the binder comprises an acidic aluminum sol and/or an alkaline silica sol, preferably an acidic aluminum sol;
the auxiliary agent comprises one or more of extrusion aid, pore-forming agent and paste;
the extrusion aid is one or more selected from starch, citric acid and sesbania powder;
the pore-forming agent is selected from one or more of polyethylene glycol, polypropylene glycol and alkylphenol ethoxylates, and is preferably alkylphenol ethoxylates;
the ointment is one or more selected from dilute nitric acid, water and ethanol, preferably dilute nitric acid and water.
Optionally, step (1) includes: kneading and extruding the IIIA group metal source, the IVB group metal oxide, the IB group metal oxide, the binder, the extrusion aid, the pore-forming agent and the paste-forming agent to form strips.
Optionally, the weight ratio of the group IIIA metal source, the group IVB metal oxide, the group IB metal oxide, the binder, the extrusion aid, the pore-forming agent and the paste forming agent is 100: (30-240): (30-250): (120-240): (30-140): (8-30): (1-120).
Optionally, the drying conditions include: the temperature is 0-200 ℃ and the time is 1-120 h;
the roasting conditions include: the temperature is 300-800 ℃ and the time is 1-48 h.
In a third aspect, the present invention provides a use of the hydrogen peroxide decomposition catalyst according to the first aspect of the present invention for the catalytic decomposition of hydrogen peroxide in an aqueous methanol solution.
Optionally, the content of hydrogen peroxide in the aqueous methanol solution is 0.01 to 1.0 weight percent, and the mass space velocity of the feed liquid of the aqueous methanol solution is 0.01 to 20h -1 Or the dosage of the hydrogen oxide decomposition catalyst is 0.5-10% of the weight of the methanol aqueous solution;
the conditions of the catalytic decomposition include: the temperature is 0-200 ℃, and the pressure is 0.1-2.0 MPa
Through the technical scheme, the lateral pressure crushing strength of the hydrogen peroxide decomposition catalyst is high, hydrogen peroxide in the methanol aqueous solution can be directly and effectively decomposed, and the catalytic decomposition effect is good; the method is simple and feasible, and the hydrogen peroxide decomposition catalyst with higher side pressure crushing strength can be prepared.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the present invention provides a hydrogen peroxide decomposition catalyst comprising 21 to 39 wt% of a group IVB metal oxide, 21 to 40 wt% of a group IB metal oxide and 21 to 58 wt% of a group IIIA metal oxide.
The hydrogen peroxide decomposition catalyst can effectively decompose hydrogen peroxide in the methanol aqueous solution, has good side pressure crushing strength, and can meet industrial requirements.
In a preferred embodiment, the hydrogen peroxide decomposition catalyst has a side crushing strength of 70 to 150N/cm, more preferably 70 to 120N/cm.
According to the present invention, the hydrogen peroxide decomposition catalyst may contain 24 to 36 wt% of a group IVB metal oxide, 24 to 36 wt% of a group IB metal oxide, and 28 to 52 wt% of a group IIIA metal oxide.
According to the present invention, the group IVB metal in the group IVB metal oxide may include one or more of titanium, zirconium and hafnium; the group IB metal in the group IB metal oxide comprises one or more of copper, silver and gold; the group IIIA metal in the group IIIA metal oxide comprises one or more of aluminum, gallium, indium and thallium.
In a preferred embodiment, the group IVB metal oxide includes one or more of titanium dioxide, zirconium oxide and hafnium oxide, preferably titanium dioxide; the group ib metal oxide is preferably copper oxide; the group IIIA metal oxide includes one or more of aluminum oxide, gallium oxide, indium oxide and thallium oxide, preferably aluminum oxide.
In a second aspect, the present invention provides a method for preparing the hydrogen peroxide decomposition catalyst according to the first aspect, the method comprising:
(1) Mixing a IIIA metal source, a IVB metal oxide, a IB metal oxide, a binder and an auxiliary agent to obtain a mixture; the group IIIA metal source comprises a group IIIA metal source hydroxide and/or a group IIIA metal oxide;
(2) The mixture is dried and calcined.
The method omits the dipping step in the existing preparation method, has simple flow and convenient preparation, can obviously reduce the energy consumption and the exhaust emission in the catalyst preparation process, ensures that the catalyst preparation process is more economical, efficient, energy-saving and environment-friendly, and can prepare the catalyst with good catalytic decomposition performance on hydrogen peroxide and high side pressure crushing strength.
According to the present invention, the group IIIA metal source may be selected from one or more of aluminum hydroxide, aluminum oxide, gallium oxide, indium oxide and thallium oxide, preferably aluminum hydroxide and aluminum oxide, and more preferably aluminum hydroxide.
According to the invention, the binder may comprise an acidic aluminium sol and/or an alkaline silica sol, preferably an acidic aluminium sol; the content of alumina in the acidic alumina sol may vary within a wide range, and may be, for example, 1 to 25% by weight. Adjuvants are well known to those skilled in the art and may include, for example, one or more of extrusion aids, pore formers, and ointments; in one embodiment, the extrusion aid is selected from one or more of starch, citric acid and sesbania powder; the pore-forming agent is selected from one or more of polyethylene glycol, polypropylene glycol and alkylphenol ethoxylates, preferably alkylphenol ethoxylates; the ointment is selected from one or more of dilute nitric acid, water and ethanol, preferably dilute nitric acid and water.
In a preferred embodiment, step (1) comprises: kneading the IIIA metal source, IVB metal oxide, IB metal oxide, adhesive, extrusion aid, pore-forming agent and paste, and extruding to form the final product.
According to the invention, the weight ratio of the amounts of group IIIA metal source, group IVB metal oxide, group IB metal oxide, binder, extrusion aid, porogen and paste forming agent may vary within a wide range and may be, for example, 100: (30-240): (30-250): (120-240): (30-140): (8-30): (1 to 120), preferably 100: (50-110): (50-130): (130-230): (40-80): (8-20): (1-10).
According to the present invention, in step (2), the drying conditions may include: the temperature is 0-200 ℃, preferably 10-150 ℃ and the time is 1-120 h, preferably 2-96 h; the roasting conditions include: the temperature is 300-800 ℃, preferably 400-700 ℃, and the time is 1-48 hours, preferably 2-36 hours. Drying and calcination are well known to those skilled in the art and may be carried out, for example, in a thermostatted oven and a muffle furnace, respectively. The firing atmosphere is not particularly limited, and may be, for example, an air atmosphere or an inert atmosphere, and the inert atmosphere may contain an inert gas, for example, nitrogen, helium, argon, or the like. In a preferred embodiment, the first mixture is dried at 10 to 20℃for 48 hours and then subjected to a first drying.
In a third aspect, the present invention provides a use of the hydrogen peroxide decomposition catalyst according to the first aspect of the present invention for the catalytic decomposition of hydrogen peroxide in an aqueous methanol solution.
According to the invention, the hydrogen peroxide content of the aqueous methanol solution is 0.01 to 1.0% by weight, preferably 0.02 to 0.6% by weight.
According to the invention, the aqueous methanol solution can be an extraction aqueous phase obtained by extracting and separating an epoxidation reaction product of the epoxidation reaction of 3-chloropropene and hydrogen peroxide. The aqueous methanol solution contains 1 to 5 weight percent of 3-chloropropene; preferably, the aqueous methanol solution is an aqueous 3-chloropropene-free aqueous methanol solution after removal of 3-chloropropene from the aqueous extraction phase.
According to the invention, the conditions for catalytic decomposition include: the temperature is 0 to 200 ℃, preferably 60 to 100 ℃, and the pressure is 0.1 to 2MPa, preferably 0.1 to 1MPa.
Catalytic decomposition of hydrogen peroxide according to the present invention may be carried out in a decomposition reactor well known to those skilled in the art, and may be, for example, one or more of a fixed bed reactor, a fluidized bed reactor and a stirred tank reactor.
In one embodiment, the hydrogen peroxide decomposition catalyst is dispersed in the decomposition reactor and flows along with the liquid, the hydrogen peroxide decomposition catalyst is used in an amount of 0.1-40% by weight of the aqueous methanol solution, the catalytic decomposition time is 0.01-24 h, preferably the hydrogen peroxide decomposition catalyst is used in an amount of 0.5-10% by weight of the aqueous methanol solution, and the catalytic decomposition time is 0.1-10 h.
In another specific embodiment, the hydrogen peroxide decomposition catalyst is fixed in the decomposition reactor, and the feed liquid time mass space velocity of the aqueous methanol solution is 0.01-20 h -1 Preferably 0.1 to 10 hours -1 。
The method has simple process and easy industrialization, can decompose most of residual hydrogen peroxide in the methanol aqueous solution before entering the methanol high-temperature rectification separation recovery tower, and can effectively eliminate the harm of higher hydrogen peroxide content in the methanol aqueous solution to the methanol high-temperature rectification separation process.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
In all examples and comparative examples, the side crushing strength of the catalyst was measured by using a ZQJ-II intelligent particle strength tester produced by Dain intelligent test mill, and the measured side crushing strength was an average value of 20 catalyst particles, referring to HG/T2782-1996 standard.
Example 1
148.10 g of aluminum hydroxide powder (alumina content 71.56 mass%, manufactured by Shandong Botai Kogyo Co., ltd.), 149.60 g of titanium dioxide powder (chemical purity reagent), 107.10 g of powdery copper oxide (analytical purity reagent), 81.00 g of starch (analytical purity reagent), 9.00 g of sesbania powder (manufactured by Henan Rankine plant gum Co., ltd.), 280.00 g of alumina sol having an alumina content of 22.69 mass%, 18.00 g of octylphenol polyoxyethylene (15) ether (OP-15, manufactured by Henan Kogyo Co., ltd.), and 12.40 g of dilute nitric acid having a nitric acid content of 2 mass% were sufficiently kneaded in a multifunctional catalyst forming machine (manufactured by Huanan Kogyo Co., ltd.), then extruded into solid cylindrical bars having a phi of 1.8mm, dried in a drying oven at 50 ℃ for 8 hours after 26 hours at 20 to 26 ℃, then cooled in a box-type electric resistance oven, and cooled for a temperature of 10 to 45.84% by 10 cm, and a temperature of 3.45% by weight, and a cooling to 45% by weight of the catalyst, and cooling to obtain a catalyst, which is cooled to obtain a wet plastic mass, and then cooled to obtain a catalyst, which has a catalyst, 4% by weight of hydrogen peroxide, and 3.35% by weight, and 3 cm, and 3% of hydrogen peroxide, and 3% by weight, and 3% by cooling.
The mass ratio of the aluminum hydroxide powder, titanium dioxide, copper oxide, acidic aluminum sol, starch to sesbania powder, OP-15 to 2 weight percent nitric acid is 100:101.0:72.3:189.1:54.7:18.3:8.4.
shaping the prepared hydrogen peroxide decomposition catalyst into short strips of 3-5 mm, and carrying out catalytic decomposition of hydrogen peroxide in a methanol aqueous solution in a fixed bed reactor, wherein the methanol aqueous solution comprises 47.893 wt% of methanol, 0.410 wt% of chloropropanol monomethyl ether and 0.114 wt% of chloropropanolGlycol and 0.496 wt% hydrogen peroxide, said chloropropanol monomethyl ether and chloropropanol being byproducts of the epoxidation reaction; the conditions of the decomposition reaction are: the feed mass hourly space velocity of the aqueous methanol solution was 3.49h -1 The decomposition temperature was 60℃and the decomposition pressure was 0.6MPa. Liquid samples of the feed and discharge were taken separately, and the mass fraction of hydrogen peroxide was determined according to the method disclosed in CN106140186a, the catalytic decomposition results of hydrogen peroxide being shown in table 1, where m HPO1 Represents the mass fraction of hydrogen peroxide before decomposition, m HPO2 Represents the mass fraction of hydrogen peroxide after decomposition, X HPO The decomposition rate of hydrogen peroxide is shown.
TABLE 1
| Continuous feed time/h | m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 2 | 0.496 | 0.004 | 99.2 |
Example 2
The hydrogen peroxide decomposition catalyst was prepared and catalytic decomposition of hydrogen peroxide in aqueous methanol solution was carried out by the method of example 1, except that the aqueous methanol solution was fed at a mass hourly space velocity of 6.18h -1 The decomposition temperature was 75℃and the decomposition pressure was 0.9MPa. The catalytic decomposition results of hydrogen peroxide are shown in Table 2.
TABLE 2
| Continuous feed time/h | m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 1.5 | 0.496 | 0.005 | 99.0 |
Example 3
The hydrogen peroxide decomposition catalyst was prepared and catalytic decomposition of hydrogen peroxide in aqueous methanol solution was carried out by the method of example 1, except that the aqueous methanol solution was fed at a mass hourly space velocity of 9.75h -1 The decomposition temperature was 90℃and the decomposition pressure was 0.9MPa. The catalytic decomposition results of hydrogen peroxide are shown in Table 3.
TABLE 3 Table 3
| Continuous feed time/h | m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 1 | 0.496 | 0.005 | 99.0 |
Example 4
125.80 g of aluminum hydroxide powder (alumina content: 71.56% by weight, manufactured by Shandong Botai Kogyo Co., ltd.), 128.12 g of titanium dioxide powder (analytically pure reagent), 149.72 g of powdery copper oxide (analytically pure reagent), 81.00 g of starch (analytically pure reagent), 9.00 g of sesbania powder (manufactured by Henan Orchiku plant gum Co., ltd.), 259.53 g of alumina sol having an alumina content of 22.69% by weight (manufactured by Hunan Kogyo Co., ltd.), 18.01 g of octylphenol polyoxyethylene (15) ether (OP-15, manufactured by Hebei Kogyo Co., ltd.) and 3.71 g of dilute nitric acid having a nitric acid content of 2% by weight were sufficiently kneaded in a multifunctional catalyst forming machine (manufactured by Huanan Kogyo Co., ltd.), then extruded into solid cylindrical bars having a phi of 1.8mm, dried in a drying oven at 50 ℃ for 18 hours after 29 hours at 20-26 ℃, then in a box-type resistance oven, and after the temperature is raised from 15 ℃ to 3.34% by weight, the catalyst is cooled to 20.35% by weight, and the composite alumina catalyst having a compression strength of 3.35% by weight is obtained by cooling the catalyst, 3.71% by weight, and the catalyst is cooled down to 3.35% by weight, and the catalyst is cooled.
The mass ratio of the aluminum hydroxide powder, titanium dioxide, copper oxide, acidic aluminum sol, starch, sesbania powder, OP-15 and 2 wt% nitric acid is 100:101.8:119.0:206.3:71.6:14.3:2.9.
Shaping the prepared composite metal oxide catalyst into short strips with the diameter of 3-5 mm, and carrying out methanol aqueous solution by adopting the method of example 3Catalytic decomposition of hydrogen peroxide, except that the aqueous methanol solution contains 51.035 wt% of methanol, 0.629 wt% of chloropropanol monomethyl ether, 0.218 wt% of chloropropanol and 0.157 wt% of hydrogen peroxide, and the conditions of the decomposition reaction are as follows: the feed mass hourly space velocity of the aqueous methanol solution was 6.08h -1 The decomposition temperature was 75℃and the decomposition pressure was 0.5MPa. The results of the catalytic decomposition of hydrogen peroxide are shown in Table 4.
TABLE 4 Table 4
| Continuous feed time/h | m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 2 | 0.157 | 0.003 | 98.1 |
Example 5
The hydrogen peroxide decomposition catalyst was prepared and catalytic decomposition of hydrogen peroxide in an aqueous methanol solution was performed by the method of example 1, except that the aqueous methanol solution contained 49.116% by weight of methanol, 0.636% by weight of chloropropanol monomethyl ether, 0.163% by weight of chloropropanol and 0.158% by weight of hydrogen peroxide, and the conditions of the decomposition reaction were: the feed mass hourly space velocity of the aqueous methanol solution was 3.50h -1 The decomposition temperature was 60℃and the decomposition pressure was 0.7MPa. The catalytic decomposition results of hydrogen peroxide are shown in Table 5.
TABLE 5
| Continuous feed time/h | m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 2 | 0.158 | 0.004 | 97.5 |
Example 6
204.01 g of aluminum hydroxide powder (aluminum oxide content: 71.56% by weight, manufactured by Shandong Botai Kogyo Co., ltd.), 106.25 g of titanium dioxide powder (analytically pure reagent), 106.52 g of powdery copper oxide (analytically pure reagent), 81.01 g of starch (analytically pure reagent), 9.00 g of sesbania powder (manufactured by Henan Orchiku plant gum Co., ltd.), 286.00 g of alumina sol having an alumina content of 22.69% by weight (manufactured by Hunan Kogyo Co., ltd.), 18.01 g of octylphenol polyoxyethylene (15) ether (OP-15, manufactured by Hebei Kogyo Wang Huagong Co., ltd.) and 18.30 g of dilute nitric acid having a nitric acid content of 2% by weight were sufficiently kneaded in a multifunctional catalyst forming machine (manufactured by Huanan Kogyo Co., ltd.) to obtain wet plastomer, then extruded into solid cylindrical bars having a phi 1.8mm, dried at a temperature of 20-26 ℃ for 28 hours in a drying oven at 50 ℃ for 18 hours, then cooled to obtain a temperature of 10.00 ℃ C. And a dry catalyst having a temperature of 10% by cooling to 60.600% by weight, and a temperature of the catalyst having a hydrogen peroxide content of 2% by weight, and a reduced concentration of nitric acid of 3% by weight, and a catalyst of hydrogen peroxide, which is cooled to obtain the wet plastomer.
The mass ratio of the aluminum hydroxide powder, titanium dioxide, copper oxide, acidic aluminum sol, starch to sesbania powder, OP-15 to 2 weight percent nitric acid is 100:52.1:52.2:140.2:44.1:8.8:9.0.
shaping the prepared hydrogen peroxide decomposition catalyst into short strips with the diameter of 3-5 mm, and carrying out catalytic decomposition of hydrogen peroxide in a methanol aqueous solution in a stirred tank reactor, wherein the methanol aqueous solution comprises 51.407 weight percent of methanol, 0.356 weight percent of chloropropanol monomethyl ether, 0.110 weight percent of chloropropanol and 0.124 weight percent of hydrogen peroxide, and the conditions of the decomposition reaction are as follows: the stirring speed is 600r/min, the decomposition temperature is 60 ℃, the decomposition pressure is 0.1MPa, the catalyst dosage is 5.00% of the mass of the methanol aqueous solution, and the decomposition time is 30min. The results of the catalytic decomposition of hydrogen peroxide are shown in Table 6.
TABLE 6
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.124 | 0.007 | 94.4 |
Example 7
A composite metal oxide catalyst was prepared by the method of example 1 and catalytic decomposition of hydrogen peroxide in an aqueous methanol solution was performed by the method of example 6, except that the aqueous methanol solution contained 48.832% by weight of methanol, 0.347% by weight of chloropropanol monomethyl ether, 0.088% by weight of chloropropanol and 0.105% by weight of hydrogen peroxide. The results of the catalytic decomposition of hydrogen peroxide are shown in Table 7.
TABLE 7
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.105 | 0.007 | 93.3 |
Comparative example 1
The same volume of glass beads having a diameter of 2 to 3mm was charged in the fixed bed reactor instead of the hydrogen peroxide decomposition catalyst prepared in example 1, and the thermal decomposition of hydrogen peroxide in aqueous methanol solution was carried out in the same manner as in example 1, and the thermal decomposition results of hydrogen peroxide are shown in Table 8.
TABLE 8
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.496 | 0.491 | 1.0 |
Comparative example 2
The same volume of glass beads having a diameter of 2 to 3mm was charged in the fixed bed reactor instead of the hydrogen peroxide decomposition catalyst prepared in example 1, and the thermal decomposition of hydrogen peroxide in an aqueous methanol solution was performed by the method of example 1, except that the decomposition temperature of hydrogen peroxide was 90℃and the thermal decomposition results of hydrogen peroxide were shown in Table 9.
TABLE 9
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.496 | 0.426 | 14.1 |
Comparative example 3
The same volume of glass beads having a diameter of 2 to 3mm was charged in the fixed bed reactor instead of the hydrogen peroxide decomposition catalyst prepared in example 1, and the thermal decomposition of hydrogen peroxide in an aqueous methanol solution was carried out by the method of example 1, except that the decomposition temperature of hydrogen peroxide was 120℃and the decomposition pressure was 1.1MPa, and the thermal decomposition results of hydrogen peroxide were shown in Table 10.
Table 10
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.496 | 0.313 | 36.9 |
Comparative example 4
The same volume of glass beads having a diameter of 2 to 3mm was charged in the fixed bed reactor instead of the hydrogen peroxide decomposition catalyst prepared in example 1, and the thermal decomposition of hydrogen peroxide in an aqueous methanol solution was carried out by the method of example 1, except that the decomposition temperature of hydrogen peroxide was 150℃and the decomposition pressure was 1.1MPa, and the thermal decomposition results of hydrogen peroxide were shown in Table 11.
TABLE 11
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.496 | 0.067 | 86.5 |
Comparative example 5
290.25 g of aluminum hydroxide powder (aluminum oxide content: 71.56% by weight, manufactured by Shandong Zibo-Tex England chemical Co., ltd.), 57.60 g of starch (analytically pure reagent), 6.40 g of sesbania powder (manufactured by Henan Orchiku plant gum Co., ltd.), 412.20 g of aluminum sol (manufactured by Hunan Kogyo feldspar oil chemical Co., ltd.), 12.81 g of octylphenol polyoxyethylene (15) ether (OP-15, manufactured by Hebei Chen Tegaku Wang Huagong auxiliary agent Co., ltd.), and 23.42 g of dilute nitric acid having a nitric acid content of 2% by weight were sufficiently kneaded in a multifunctional catalyst forming machine (manufactured by Henan England chemical Co., ltd.), then extruded into solid cylindrical strips of phi 1.8mm, dried for 24 hours at 20 to 26 ℃ C, dried in a drying oven at 55 ℃ C., then in a box-type resistance oven, heated from 20 ℃ C. To 120 ℃ C., and left for 2 hours, then left at 60 ℃ C., and left at 600 ℃ C., and left for 30 hours, and after that the catalyst containing crushed aluminum catalyst having a specific strength of N is obtained by crushing.
The prepared alumina catalyst was shaped into 3-5 mm short strips, and catalytic decomposition of hydrogen peroxide in aqueous methanol solution was carried out by the method of example 7, and the catalytic decomposition results of hydrogen peroxide are shown in Table 12.
Table 12
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.105 | 0.083 | 21.0 |
Comparative example 6
The alumina catalyst was prepared and catalytic decomposition of hydrogen peroxide in aqueous methanol was carried out by the method of comparative example 5, except that the decomposition temperature of hydrogen peroxide was 75℃and the decomposition pressure was 0.2MPa, and the catalytic decomposition results of hydrogen peroxide are shown in Table 13.
TABLE 13
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.105 | 0.061 | 41.9 |
Comparative example 7
61.50 g of aluminum hydroxide powder (alumina content: 71.56% by weight, manufactured by Shandong Botai Kogyo Co., ltd.), 322.60 g of titanium dioxide powder (chemical purity reagent), 90.10 g of starch (analytical purity reagent), 10.00 g of sesbania powder (manufactured by Henan Orchiku plant gum Co., ltd.), 158.00 g of alumina sol having an alumina content of 22.69% by weight (manufactured by Hunan Kogyo Co., ltd.), 20.00 g of octylphenol polyoxyethylene (15) ether (OP-15, manufactured by Hebei Chemie, wang Huagong auxiliary Co., ltd.), and 78.30 g of dilute nitric acid having a nitric acid content of 2% by weight were sufficiently kneaded in a multifunctional catalyst forming machine (manufactured by Wanan Kogyo Co., ltd.), then extruded into solid cylindrical bars of phi 1.8mm, dried at 10-16 ℃ for 72 hours, dried at 55 ℃ for 12 hours, then placed in a box-type resistance furnace, heated from 10 ℃ to 120 ℃ for 12 minutes and left to stand at 3 ℃ for 62 ℃ for 62.600 cm, and cooled to obtain a catalyst of hydrogen peroxide having a specific weight of which is decomposed at 62% by weight.
The prepared hydrogen peroxide decomposition catalyst was shaped into 3-5 mm short strips, and the catalytic decomposition of hydrogen peroxide in aqueous methanol solution was carried out by the method of example 7, and the catalytic decomposition results of hydrogen peroxide are shown in Table 14.
TABLE 14
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.105 | 0.058 | 44.8 |
Comparative example 8
A hydrogen peroxide decomposition catalyst was prepared and catalytic decomposition of hydrogen peroxide in an aqueous methanol solution was performed by the method of comparative example 7, except that the decomposition temperature of hydrogen peroxide was 75℃and the decomposition pressure was 0.2MPa, and the catalytic decomposition results of hydrogen peroxide are shown in Table 15.
TABLE 15
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.105 | 0.030 | 71.4 |
Comparative example 9
300.05 g of aluminum hydroxide powder (alumina content 69.2% by mass, produced by Hunan long catalyst mill), 53.54 g of titanium dioxide (chemical purity reagent) having a titanium dioxide content of 98% by mass, 60.00 g of starch (analytical purity reagent), 7.50 g of sesbania powder (produced by Henan Rankine plant gum mill), 422.38 g of alumina sol having an alumina content of 22.4% by mass (produced by Hunan Seto oil chemical Co., ltd.), 22.51 g of octylphenol polyoxyethylene (15) ether (OP-15, produced by Hechen bench Wang Huagong auxiliary Co., ltd.), and 49.54 g of dilute nitric acid having a nitric acid content of 2.0% by mass were sufficiently kneaded in a multifunctional catalyst forming machine (produced by Henan chemical industry Co., ltd.), then extruded into solid cylindrical bars having a phi of 1.8mm, dried at 24 to 28 ℃ C. For 27 hours, dried at 50 ℃ C. For 4 hours, then placed in a box-type resistance furnace, heated at a rate of 120 ℃ C./3 to 550% by mass/550% by mass of alumina, and cooled at a rate of 120 ℃ C. To a temperature of 14% by mass, and heated to a temperature of the catalyst of 14% by natural cooling, which is obtained.
30.00 g of a cylindrical bar catalyst containing 14.80 mass% titanium oxide and 85.20 mass% aluminum oxide was impregnated with 50.00 g of an aqueous solution in which 2.485 g of ammonium molybdate tetrahydrate and 3.400 g of copper nitrate trihydrate were dissolved at 25 to 30℃for 24 hours, then the impregnated product was dried at 105℃for 12 hours, then the dried product was calcined at 550℃for 16 hours, and after natural cooling, a cylindrical bar composite metal oxide catalyst containing 13.39 mass% titanium oxide, 6.11 mass% molybdenum trioxide, 3.38 mass% copper oxide and 77.12 mass% aluminum oxide was obtained, the side pressure crushing strength of the catalyst was 48.7N/cm.
The weight ratio of the dosage of the aluminum hydroxide powder, the titanium dioxide, the acidic aluminum sol, the starch and sesbania powder, the OP-15 and 2 weight percent of nitric acid is 100:17.8:140.8:22.5:7.5:16.5.
the prepared hydrogen peroxide decomposition catalyst was subjected to decomposition of hydrogen peroxide in a methanol aqueous solution in a stirred tank reactor under the same conditions as in example 7, and the decomposition results of hydrogen peroxide are shown in Table 16.
Table 16
| m HPO1 /％ | m HPO2 /％ | X HPO /％ |
| 0.105 | 0.007 | 93.3 |
From the above, the method of the invention can reduce the mass fraction of hydrogen peroxide in the methanol aqueous solution from 0.105-0.496% to below 0.01% under the conditions of the examples, and the side pressure crushing strength of the catalyst is higher than 70N/cm, so that the catalyst is not easy to crush, and the strength requirement of the industrial fixed bed reactor on the catalyst filling can be met. By contrast, the mass fraction of hydrogen peroxide in the aqueous methanol solution cannot be reduced to less than 0.01% under most conditions by adopting the method of the comparative example, and even if the mass fraction of hydrogen peroxide in the aqueous methanol solution can be reduced to less than 0.01%, the side crushing strength of the catalyst is remarkably lower than 70N/cm, so that the catalyst is easy to crush, and the strength requirement of the industrial fixed bed reactor on the packed catalyst is difficult to meet.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (9)
1. A hydrogen peroxide decomposition catalyst comprising 21 to 39 wt.% group ivb metal oxide, 21 to 40 wt.% group ib metal oxide, and 21 to 58 wt.% group iiia metal oxide; the lateral pressure crushing strength of the hydrogen peroxide decomposition catalyst is 70-150N/cm; the metal in the IVB metal oxide is titanium, the IB metal in the IB metal oxide is copper, and the IIIA metal in the IIIA metal oxide is aluminum;
the hydrogen peroxide decomposition catalyst is applied to the catalytic decomposition of hydrogen peroxide in a methanol aqueous solution; the aqueous methanol solution is an aqueous methanol solution which does not contain 3-chloropropene after 3-chloropropene is removed from an extraction aqueous phase; the conditions of the catalytic decomposition include: the temperature is 60-100 ℃ and the pressure is 0.1-0.6 MPa;
the hydrogen peroxide decomposition catalyst is prepared by the following method:
(1) Kneading a IIIA metal source, a IVB metal oxide, a IB metal oxide, a binder, an extrusion aid, a pore-forming agent and a paste, extruding the paste into strips, and forming to obtain a mixture; the group IIIA metal source comprises a group IIIA metal source hydroxide and/or a group IIIA metal oxide;
(2) The mixture is dried and calcined.
2. The hydrogen peroxide decomposition catalyst according to claim 1, wherein the hydrogen peroxide decomposition catalyst has a side crushing strength of 70 to 120N/cm.
3. The hydrogen peroxide decomposition catalyst according to claim 1, wherein the hydrogen peroxide decomposition catalyst comprises 24 to 36 wt.% group ivb metal oxide, 24 to 36 wt.% group ib metal oxide, and 28 to 52 wt.% group iiia metal oxide.
4. A hydrogen peroxide decomposition catalyst according to any one of claims 1 to 3, wherein the group ivb metal oxide titania;
the IB group metal oxide is copper oxide;
the group IIIA metal oxide is alumina.
5. The hydrogen peroxide decomposition catalyst of claim 1, wherein the binder comprises an acidic aluminum sol and/or an alkaline silica sol;
the extrusion aid is one or more selected from starch, citric acid and sesbania powder;
the pore-forming agent is one or more selected from polyethylene glycol, polypropylene glycol and alkylphenol ethoxylates;
the ointment is one or more selected from dilute nitric acid, water and ethanol.
6. The hydrogen peroxide decomposition catalyst of claim 5, the binder being an acidic aluminum sol; the pore-forming agent is alkylphenol polyoxyethylene; the ointment is diluted nitric acid and water.
7. The hydrogen peroxide decomposition catalyst of claim 1, wherein the group iiia metal source, the group ivb metal oxide, the group ib metal oxide, the binder, the extrusion aid, the porogen, and the paste forming amount are present in a weight ratio of 100: (30-240): (30-250): (120-240): (30-140): (8-30): (1-120).
8. The hydrogen peroxide decomposition catalyst of claim 1, wherein the drying conditions comprise: the temperature is 0-200 ℃ and the time is 1-120 h;
the roasting conditions include: the temperature is 300-800 ℃ and the time is 1-48 h.
9. The hydrogen peroxide decomposition catalyst according to claim 1, wherein the hydrogen peroxide content in the aqueous methanol solution is 0.01 to 1.0 wt%, and the feed liquid hourly space velocity of the aqueous methanol solution is 0.01 to 20h -1 Alternatively, the hydrogen peroxide decomposition catalyst is used in an amount of 0.5 to 10% by weight based on the aqueous methanol solution.
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| CN102259023A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve catalyst and preparation method and use thereof |
| CN106140186A (en) * | 2015-04-18 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of method of decomposition of hydrogen peroxide in decomposition catalyst and epoxidation reaction product thereof |
| CN110935432A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Titanium oxide-aluminum oxide composite oxide and preparation method thereof |
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