CN108722409A - Mesoporous copper-based aluminium oxide catalyst, preparation method and application - Google Patents
Mesoporous copper-based aluminium oxide catalyst, preparation method and application Download PDFInfo
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- CN108722409A CN108722409A CN201810390194.9A CN201810390194A CN108722409A CN 108722409 A CN108722409 A CN 108722409A CN 201810390194 A CN201810390194 A CN 201810390194A CN 108722409 A CN108722409 A CN 108722409A
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- copper
- aluminium oxide
- oxide catalyst
- mesoporous
- based aluminium
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 253
- 239000010949 copper Substances 0.000 title claims abstract description 103
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 71
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 24
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 7
- 150000001621 bismuth Chemical class 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- -1 isobutanol aluminum Chemical compound 0.000 claims 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 claims description 4
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- 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 claims description 3
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000008187 granular material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NMTBZBPWKJALHU-UHFFFAOYSA-N O=C.C#C Chemical compound O=C.C#C NMTBZBPWKJALHU-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- ILMMCBFQWHPTHE-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O.CCCC(O)O ILMMCBFQWHPTHE-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FDKCTEWMJWRPDS-UHFFFAOYSA-N dialuminum;trimagnesium;trisilicate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] FDKCTEWMJWRPDS-UHFFFAOYSA-N 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052832 pyrope Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000010457 zeolite 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
- B01J23/72—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
-
- 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
-
- B01J35/23—
-
- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a kind of mesoporous copper-based aluminium oxide catalyst, preparation method and application, preparation method includes：Copper source and template are dissolved in organic solvent, precursor solution is obtained；Silicon source and acid are dissolved in organic solvent, carrier solution is obtained；The precursor solution and carrier solution are mixed, stirring, aging, calcining obtains mesoporous copper-based aluminium oxide catalyst.The active good, high selectivity of mesoporous copper-based aluminium oxide catalyst of the present invention, the advantages that intensity is high, easily separated, catalyst granules is uniform, easily-activated, preparation method is simple for catalyst, reproducible, and economic and technical performance is very notable.
Description
Technical field
The present invention relates to a kind of field of catalyst preparation, more particularly to a kind of mesoporous copper-based aluminium oxide catalyst, preparation
Method and its application.
Background technology
With the development of world economy, the fields such as weaving, medicine, chemical industry, auto industry are fast-developing, as wherein important
The demand of the 1,4-butanediol of raw material also increases year by year.Production 1,4-butanediol has oil and coal two lines.The former with
Butane method and butylene method are representative, such method route is relatively complicated, but energy consumption is relatively low, are suitble to using oil as the state of main resource
Family is produced；The latter refers to acetylene-formaldehyde process, and this method route is simple, and conversion ratio and yield are higher, but energy consumption is higher, is suitble to coal money
The abundant countries and regions in source use.China has abundant coal resources, and 1,4-butanediol tool is prepared by acetylene-formaldehyde process technique
There is advantageous advantage, so China prepares 1,4-butanediol based on acetylene formolation synthetic route.Currently, preparing Isosorbide-5-Nitrae-
In two steps, first, formaldehyde and acetylene reaction synthesize Isosorbide-5-Nitrae-butynediols, but Isosorbide-5-Nitrae-butynediols Hydrogenation is for Isosorbide-5-Nitrae-for butanediol
Butanediol.In synthesis Isosorbide-5-Nitrae-butynediols reaction, using formaldehyde and acetylene as raw material, using copper-based catalysts.In reaction process
In, Cu2+Cu is first restored by HCHO+, then Cu+It interacts with acetylene and generates alkynes copper complex activated centre.
Currently, the copper-based catalysts industrially used are divided into no-load build catalyst and loaded catalyst.No-load build
Catalyst includes malachite, cupric pyrope, CuO-Bi2O3Nano-powder etc..The catalyst of the type is mostly prepared with the precipitation method,
Copper component dispersion degree is poor, and effective rate of utilization is low, and intolerant to wearing and being easy to reunite, active component is easy to run off, and is not particularly suitable for starching
State bed process is developed.For such case, it has been developed that with diatomite, zeolite, Al2O3Deng the supported catalyst for carrier
Agent.Carried copper bismuth catalyst is mostly prepared with infusion process, but with copper component strong interaction occurs for such catalyst carrier, living
Change difficulty, copper component is difficult to by effective activation be alkynes copper complex activated centre；Carrier is first prepared, is lived afterwards using infusion process load
Property component, increases operating process and cost.
Invention content
It is a primary object of the present invention to provide a kind of novel mesoporous copper-based aluminium oxide catalyst, preparation method and answer
With the technical problem to be solved is that making, the active good, high selectivity of its catalyst, intensity be high, easily separated, catalyst granules
Uniformly, easily-activated, thus more suitable for practicality.
The object of the invention to solve the technical problems is realized using following technical scheme.It proposes according to the present invention
A kind of mesoporous copper-based aluminium oxide catalyst preparation method comprising：
Copper source and template are dissolved in organic solvent, precursor solution is obtained；
Silicon source and acid are dissolved in organic solvent, carrier solution is obtained；
The precursor solution and carrier solution are mixed, stirring, aging, calcining obtains mesoporous copper-based aluminium oxide and urges
Agent.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, the preparation method of mesoporous copper-based aluminium oxide catalyst above-mentioned, wherein also being wrapped in the carrier solution
Include bismuth salt；The bismuth salt is at least one of bismuth nitrate, bismuth sulfate and bismuth acetate.
Preferably, the preparation method of mesoporous copper-based aluminium oxide catalyst above-mentioned, wherein the copper source is acetylacetone,2,4-pentanedione
At least one of copper, copper nitrate, copper sulphate and copper acetate；
The template is P123 or F127；
The silicon source is at least one of aluminium isopropoxide, isobutanol aluminum, aluminium secondary butylate and aluminum isopropylate；
The acid is nitric acid, sulfuric acid or acetic acid；
The organic solvent is ethyl alcohol, methanol or acetone.
Preferably, the preparation method of mesoporous copper-based aluminium oxide catalyst above-mentioned, wherein the mixing time is 5-
12h；
The aging temperature is 50-80 DEG C, ageing time 1-3d；
The calcination temperature is 400-1200 DEG C, and heating rate is 0.5-5 DEG C/min, calcination time 4-6h.
Preferably, the preparation method of mesoporous copper-based aluminium oxide catalyst above-mentioned, wherein the mesoporous copper-based aluminium oxide
The content of copper is 20-30wt% in catalyst.
Preferably, the preparation method of mesoporous copper-based aluminium oxide catalyst above-mentioned, wherein the mesoporous copper-based aluminium oxide
The content of bismuth is 0-6wt% in catalyst.
The object of the invention to solve the technical problems is also realized using technical solution below.It proposes according to the present invention
The mesoporous copper-based aluminium oxide catalyst of one kind, be prepared by method above-mentioned；The mesoporous copper-based aluminium oxide catalyst
Active component is copper oxide, carrier Al2O3。
The object of the invention to solve the technical problems is also realized using technical solution below.It proposes according to the present invention
A kind of mesoporous copper-based aluminium oxide catalyst application, mesoporous copper-based aluminium oxide catalyst above-mentioned is activated, catalysis formaldehyde and
Acetylene synthesizes 1,4- butynediols.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, the application of mesoporous copper-based aluminium oxide catalyst above-mentioned, wherein the mesoporous copper-based alumina catalyzation
The application of agent includes：The mesoporous copper-based aluminium oxide catalyst and formalin are placed in reactor, are passed through protective gas, is risen
Temperature is passed through acetylene to 60-75 DEG C, activates 2-5h；It is warming up to 85-95 DEG C, carries out the ethynylation of formaldehyde, obtains Isosorbide-5-Nitrae-butine
Glycol.
Preferably, the application of mesoporous copper-based aluminium oxide catalyst above-mentioned, wherein the mass fraction of the formalin
For 4-40%；
The mass ratio of the mesoporous copper-based aluminium oxide catalyst and formalin is 1:5-100；
The protective gas is nitrogen or argon gas；
The acetylene pressure is 0.04-0.2MPa.
By above-mentioned technical proposal, under the mesoporous copper-based aluminium oxide catalyst of the present invention, preparation method and application at least have
Row advantage：
1) mesoporous copper-based aluminium oxide catalyst is prepared by one step of alcohol induced self-assembly method in the present invention, avoids leaching
Stain process simplifies operating process, while Al in self assembling process2O3Suitable interaction is formed with copper component, makes Cu2+Quilt
Effectively it is reduced to Cu+, then acted on acetylene and generate more alkynes copper complexs activated centre；Catalyst is with mesoporous Al2O3For
Carrier improves the specific surface area and abrasion resistance properties of the dispersion degree catalyst of copper activity component, leads to active catalyst sites
Increase, increases with the contact area of reaction solution when reaction, high activity and selectivity to make catalyst show.The application's
Slurry reactor of the mesoporous copper-based aluminium oxide catalyst for formaldehyde and acetylene synthesis Isosorbide-5-Nitrae-butynediols, formaldehyde conversion are more than
85%, butynediols is selectively more than 88%.
2) the active good, high selectivity of catalyst of the invention, intensity are high, easily separated, catalyst granules is uniform, easily living
The advantages that change, preparation method is simple for catalyst, reproducible, and economic and technical performance is very notable.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, it is described in detail as after with presently preferred embodiments of the present invention below.
Specific implementation mode
It is of the invention to reach the technological means and effect that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to propose according to the present invention mesoporous copper-based aluminium oxide catalyst, preparation method and application its specific embodiment party
Formula, structure, feature and its effect are described in detail as after.In the following description, different " embodiment " or " embodiment " refers to
It is not necessarily the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be by any suitable shape
Formula combines.
A kind of preparation method for mesoporous copper-based aluminium oxide catalyst that one embodiment of the present of invention proposes comprising：
Copper source and template are dissolved in organic solvent, precursor solution is obtained；
Silicon source, bismuth salt and acid are dissolved in organic solvent, carrier solution is obtained；
The precursor solution and carrier solution are mixed with vigorous stirring, persistently stir 5-12h, 50-80 DEG C old
Change 1-3d, calcining obtains mesoporous copper-based aluminium oxide catalyst.
Preferably, in carrier solution further include bismuth salt；The bismuth salt be bismuth nitrate, bismuth sulfate and bismuth acetate at least
It is a kind of.
Preferably, copper source is at least one of acetylacetone copper, copper nitrate, copper sulphate and copper acetate；
Template is P123 or F127；
Silicon source is at least one of aluminium isopropoxide, isobutanol aluminum, aluminium secondary butylate and aluminum isopropylate；
Acid is nitric acid, sulfuric acid or acetic acid；
Organic solvent is ethyl alcohol, methanol or acetone.
Preferably, calcination temperature is 400-1200 DEG C, and heating rate is 0.5-5 DEG C/min, calcination time 4-6h.
Preferably, the content of copper is 20-30wt% in mesoporous copper-based aluminium oxide catalyst；The content of bismuth is 0-6wt%.
The object of the invention to solve the technical problems is also realized using technical solution below.It proposes according to the present invention
The mesoporous copper-based aluminium oxide catalyst of one kind, be prepared by method above-mentioned；The mesoporous copper-based aluminium oxide catalyst
Active component is copper oxide, and auxiliary agent is bismuth oxide, carrier Al2O3。
Another embodiment of the present invention proposes a kind of mesoporous copper-based aluminium oxide catalyst, is prepared by method above-mentioned；
The active component of the mesoporous copper-based aluminium oxide catalyst is copper oxide, and auxiliary agent is bismuth oxide, carrier Al2O3。
Another embodiment of the present invention proposes a kind of application of mesoporous copper-based aluminium oxide catalyst, will be above-mentioned mesoporous copper-based
Slurry reactor of the aluminium oxide catalyst for formaldehyde and acetylene synthesis Isosorbide-5-Nitrae-butynediols；By mesoporous copper-based aluminium oxide catalyst
It is placed in reactor with formalin, protective gas is passed through and drains air in reactor, while examining the air-tightness of reactor to protect
Demonstrate,prove experiment safety；It is warming up to 60-75 DEG C, acetylene is passed through and empties protective gas, activates 2-5h；85-95 DEG C is warming up to after activation,
The ethynylation for carrying out formaldehyde, obtains Isosorbide-5-Nitrae-butynediols.After reaction, turn off reactor, reaction solutions is waited to be cooled to room
Temperature.Isosorbide-5-Nitrae-butynediols quantitative analysis is carried out using gas-chromatography.The quality of residual formaldehyde is quantified by iodimetric titration.
Preferably, the mass fraction of formalin is 4-40%；
Mesoporous copper-based aluminium oxide catalyst and the mass ratio of formalin are 1:5-100；
Protective gas is nitrogen or argon gas；
Acetylene pressure is 0.04-0.2MPa.
Embodiment 1
A kind of preparation method for mesoporous copper-based aluminium oxide catalyst that one embodiment of the present of invention proposes comprising：
2g P123 and 0.7701g copper nitrates are dissolved in 20mL absolute ethyl alcohols, precursor solution is obtained；
The aluminium isopropoxide of 0.02mol is added in 20mL absolute ethyl alcohols, and the nitric acid of 3.3mL 67wt% is added, is stirred
Dissolving, obtains carrier solution；
With vigorous stirring, carrier solution is added in precursor solution and carrier solution, 12h is persistently stirred, in 50-80
Aging 2d makes ethyl alcohol slow evaporation obtain gel-like product to be warming up to 1 DEG C/min heating rates in Muffle furnace in DEG C baking oven
500 DEG C, 5h is calcined, mesoporous copper-based aluminium oxide catalyst is obtained.
Another embodiment of the present invention proposes a kind of mesoporous copper-based aluminium oxide catalyst, by the method preparation of embodiment 1
?；The active component of the mesoporous copper-based aluminium oxide catalyst is copper oxide, carrier Al2O3。
Another embodiment of the present invention proposes a kind of application of mesoporous copper-based aluminium oxide catalyst, by the mesoporous of embodiment 1
Slurry reactor of the copper-based aluminium oxide catalyst for formaldehyde and acetylene synthesis Isosorbide-5-Nitrae-butynediols；Mesoporous copper-based aluminium oxide is urged
Agent and the formalin of 4wt% are 1 in mass ratio:100 are placed in reactor, are passed through nitrogen and drain air in reactor, simultaneously
Examine the air-tightness of reactor to ensure experiment safety；75 DEG C are warming up to, is passed through acetylene by nitrogen purge, acetylene pressure is
0.04MPa activates 2h；It is warming up to 85 DEG C after activation, carries out the ethynylation of formaldehyde, obtains Isosorbide-5-Nitrae-butynediols.Reaction knot
Shu Hou turns off reactor, and reaction solutions is waited to be cooled to room temperature.Isosorbide-5-Nitrae-butynediols quantitative analysis is carried out using gas-chromatography.It is remaining
The quality of formaldehyde is quantified by iodimetric titration.The evaluation result of the mesoporous copper-based aluminium oxide catalyst of embodiment 1 is as shown in table 1.
Embodiment 2
A kind of preparation method for mesoporous copper-based aluminium oxide catalyst that one embodiment of the present of invention proposes comprising：
It is dissolved in 10mL absolute ethyl alcohols by 1g P123 and with 0.5215g acetylacetone coppers, obtains precursor solution；
The aluminium isopropoxide of 0.01mol is added in 10mL absolute ethyl alcohols, and the nitric acid of 1.7mL 67wt% is added, is stirred
Dissolving, obtains carrier solution；
With vigorous stirring, carrier solution is added in precursor solution and carrier solution, persistently stirs 5h, dried at 60 DEG C
Aging 2d makes ethyl alcohol slow evaporation acquisition gel-like product be warming up to 1200 in Muffle furnace with 3 DEG C/min heating rates in case
DEG C, 4h is calcined, mesoporous copper-based aluminium oxide catalyst is obtained.
Another embodiment of the present invention proposes a kind of mesoporous copper-based aluminium oxide catalyst, by the method preparation of embodiment 2
?；The active component of the mesoporous copper-based aluminium oxide catalyst is copper oxide, carrier Al2O3。
Another embodiment of the present invention proposes a kind of application of mesoporous copper-based aluminium oxide catalyst, by the mesoporous of embodiment 2
Slurry reactor of the copper-based aluminium oxide catalyst for formaldehyde and acetylene synthesis Isosorbide-5-Nitrae-butynediols；Mesoporous copper-based aluminium oxide is urged
Agent and the formalin of 40wt% are 1 in mass ratio:5 are placed in reactor, are passed through nitrogen and drain air in reactor, examine simultaneously
The air-tightness of reactor is tested to ensure experiment safety；60 DEG C are warming up to, is passed through acetylene by nitrogen purge, acetylene pressure is
0.20MPa activates 5h；It is warming up to 90 DEG C after activation, carries out the ethynylation of formaldehyde, obtains Isosorbide-5-Nitrae-butynediols.Reaction knot
Shu Hou turns off reactor, and reaction solutions is waited to be cooled to room temperature.Isosorbide-5-Nitrae-butynediols quantitative analysis is carried out using gas-chromatography.It is remaining
The quality of formaldehyde is quantified by iodimetric titration.The evaluation result of the mesoporous copper-based aluminium oxide catalyst of embodiment 2 is as shown in table 1.
Embodiment 3
A kind of preparation method for mesoporous copper-based aluminium oxide catalyst that one embodiment of the present of invention proposes comprising：
It is dissolved in 10mL absolute ethyl alcohols by 1g P123 and with 0.5215g acetylacetone coppers, obtains precursor solution；
The aluminium isopropoxide of 0.01mol and 0.0493g bismuth nitrates are added in 10mL absolute ethyl alcohols, and 1.7mL is added
The nitric acid of 67wt%, stirring and dissolving obtain carrier solution；
With vigorous stirring, carrier solution is added in precursor solution and carrier solution, persistently stirs 5h, dried at 60 DEG C
Aging 2d makes ethyl alcohol slow evaporation acquisition gel-like product be warming up to 1200 in Muffle furnace with 3 DEG C/min heating rates in case
DEG C, 4h is calcined, mesoporous copper-based aluminium oxide catalyst is obtained.
Another embodiment of the present invention proposes a kind of mesoporous copper-based aluminium oxide catalyst, by the method preparation of embodiment 2
?；The active component of the mesoporous copper-based aluminium oxide catalyst is copper oxide, and auxiliary agent is bismuth oxide, carrier Al2O3。
Another embodiment of the present invention proposes a kind of application of mesoporous copper-based aluminium oxide catalyst, by the mesoporous of embodiment 3
Slurry reactor of the copper-based aluminium oxide catalyst for formaldehyde and acetylene synthesis Isosorbide-5-Nitrae-butynediols；Mesoporous copper-based aluminium oxide is urged
Agent and the formalin of 40wt% are 1 in mass ratio:5 are placed in reactor, are passed through nitrogen and drain air in reactor, examine simultaneously
The air-tightness of reactor is tested to ensure experiment safety；60 DEG C are warming up to, is passed through acetylene by nitrogen purge, acetylene pressure is
0.20MPa activates 5h；It is warming up to 90 DEG C after activation, carries out the ethynylation of formaldehyde, obtains Isosorbide-5-Nitrae-butynediols.Reaction knot
Shu Hou turns off reactor, and reaction solutions is waited to be cooled to room temperature.Isosorbide-5-Nitrae-butynediols quantitative analysis is carried out using gas-chromatography.It is remaining
The quality of formaldehyde is quantified by iodimetric titration.The evaluation result of the mesoporous copper-based aluminium oxide catalyst of embodiment 3 is as shown in table 1.
The mesoporous copper-based aluminium oxide catalyst of table 1 catalyzes and synthesizes the evaluation result of the slurry reactor of Isosorbide-5-Nitrae-butynediols
| Sample number into spectrum | Formaldehyde conversion % | Butynediols selectivity % | Propilolic alcohol selectivity % |
| Embodiment 1 | 85.6 | 88.9 | 10.3 |
| Embodiment 2 | 88.5 | 90.3 | 8.7 |
| Embodiment 3 | 96.7 | 97.2 | 2.1 |
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to the technical spirit of the present invention to any simple modification, equivalent change and modification made by above example, this hair is still fallen within
In the range of bright technical solution.
Claims (10)
1. a kind of preparation method of mesoporous copper-based aluminium oxide catalyst, which is characterized in that it includes：
Copper source and template are dissolved in organic solvent, precursor solution is obtained；
Silicon source and acid are dissolved in organic solvent, carrier solution is obtained；
The precursor solution and carrier solution are mixed, stirring, aging, calcining obtains mesoporous copper-based aluminium oxide catalyst.
2. the preparation method of mesoporous copper-based aluminium oxide catalyst according to claim 1, which is characterized in that the carrier
It further include bismuth salt in solution；The bismuth salt is at least one of bismuth nitrate, bismuth sulfate and bismuth acetate.
3. the preparation method of mesoporous copper-based aluminium oxide catalyst according to claim 1, which is characterized in that the copper source
For at least one of acetylacetone copper, copper nitrate, copper sulphate and copper acetate；
The template is P123 or F127；
The silicon source is at least one of aluminium isopropoxide, isobutanol aluminum, aluminium secondary butylate and aluminum isopropylate；
The acid is nitric acid, sulfuric acid or acetic acid；
The organic solvent is ethyl alcohol, methanol or acetone.
4. the preparation method of mesoporous copper-based aluminium oxide catalyst according to claim 1, which is characterized in that the stirring
Time is 5-12h；
The aging temperature is 50-80 DEG C, ageing time 1-3d；
The calcination temperature is 400-1200 DEG C, and heating rate is 0.5-5 DEG C/min, calcination time 4-6h.
5. the preparation method of mesoporous copper-based aluminium oxide catalyst according to claim 1, which is characterized in that described is mesoporous
The content of copper is 20-30wt% in copper-based aluminium oxide catalyst.
6. the preparation method of mesoporous copper-based aluminium oxide catalyst according to claim 2, which is characterized in that described is mesoporous
The content of bismuth is 0-6wt% in copper-based aluminium oxide catalyst.
7. a kind of mesoporous copper-based aluminium oxide catalyst, which is characterized in that by the preparation of claim 1-6 any one of them methods
?；The active component of the mesoporous copper-based aluminium oxide catalyst is copper oxide, carrier Al2O3。
8. a kind of application of mesoporous copper-based aluminium oxide catalyst, which is characterized in that by the mesoporous copper-based oxidation described in claim 7
Al catalysts activate, and are catalyzed formaldehyde and acetylene synthesizes Isosorbide-5-Nitrae-butynediols.
9. the application of mesoporous copper-based aluminium oxide catalyst according to claim 8, which is characterized in that described is mesoporous copper-based
The application of aluminium oxide catalyst includes：The mesoporous copper-based aluminium oxide catalyst and formalin are placed in reactor, are passed through
Protective gas is warming up to 60-75 DEG C, is passed through acetylene, activates 2-5h；It is warming up to 85-95 DEG C, carries out the ethynylation of formaldehyde,
Obtain 1,4- butynediols.
10. the application of mesoporous copper-based aluminium oxide catalyst according to claim 9, which is characterized in that the formaldehyde is molten
The mass fraction of liquid is 4-40%；
The mass ratio of the mesoporous copper-based aluminium oxide catalyst and formalin is 1:5-100；
The protective gas is nitrogen or argon gas；
The acetylene pressure is 0.04-0.2MPa.
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| CN112191247A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | Cu/mesoporous aluminum oxide catalyst and preparation and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109317188A (en) * | 2018-11-14 | 2019-02-12 | 福州大学 | A kind of preparation method and application of mesoporous FeCu-ZSM-5 molecular sieve |
| CN112191247A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | Cu/mesoporous aluminum oxide catalyst and preparation and application thereof |
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