CN105597756A - Copper-based core-shell catalyst for preparing methyl formate through methyl alcohol dehydrogenation and preparation method and application thereof - Google Patents
Copper-based core-shell catalyst for preparing methyl formate through methyl alcohol dehydrogenation and preparation method and application thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 165
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 239000010949 copper Substances 0.000 title claims abstract description 28
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 27
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 36
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 156
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000002245 particle Substances 0.000 claims abstract description 101
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 65
- 239000005751 Copper oxide Substances 0.000 claims abstract description 58
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 58
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- 229960004643 cupric oxide Drugs 0.000 claims description 103
- 238000006243 chemical reaction Methods 0.000 claims description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 238000011084 recovery Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 229910021426 porous silicon Inorganic materials 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- 239000012452 mother liquor Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- -1 alkyl silicate Chemical compound 0.000 claims description 7
- 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 7
- 239000004088 foaming agent Substances 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 230000008569 process Effects 0.000 description 17
- 230000009467 reduction Effects 0.000 description 17
- 235000013339 cereals Nutrition 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017929 Cu—SiO2 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- IDTSWOFPBZZRSY-UHFFFAOYSA-N [Cu].COC=O Chemical compound [Cu].COC=O IDTSWOFPBZZRSY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 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
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- 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
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/394—
-
- B01J35/396—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/651—
-
- B01J35/653—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
Abstract
The invention provides a copper-based core-shell catalyst for preparing methyl formate through methyl alcohol dehydrogenation. The copper-based core-shell catalyst is composed of copper oxide nano-particles and mesoporous silica. The copper oxide nano-particles are covered with a mesoporous silica shell layer. The content of copper oxide is 5 wt% to 70 wt%, the particle size is smaller than 10 nm, and dispersity is 5.0% to 30.0%. The content of mesoporous silica is 30 wt% to 95 wt%, the average hole diameter of holes in the mesoporous silica shell layer is 2.0 nm to 5.0 nm, the specific area is 100 m<2>/g to 1,000 m<2>/g, and the thickness of the shell layer is 10 nm to 400 nm. The size of nanometer copper oxide@mesoporous silica core-shell microspheres is 200 nm to 1,000 nm. The copper-based core-shell catalyst has the advantages of being good in stability and long in catalysis service life.
Description
Technical field
The invention belongs to a kind of preparation method and application of copper base nucleocapsid catalyst, relate to specifically a kind of usingIn copper base nucleocapsid catalyst and the preparation method and application of methanol dehydrogenation methyl formate processed.
Background technology
Methyl formate is the important intermediate of producing the chemicals such as formic acid, formamide. Industrial, methyl formateMainly prepare by carbonylation of methanol liquid phase reactor, but the method is high to material purity requirement, and methanol conversionRate is low, reaction pressure is high, catalyst separation is difficult. Consider the more and more severeer energy and environmental problem,In recent years, research finds that it is the catalytic process that has very much application prospect that methanol dehydrogenation is prepared methyl formate, is expected toDevelop into green, economy, prepare efficiently the method for methyl formate.
As important transition metal oxide, copper oxide nano material due to cheap, catalytic activity is high andGood selective is widely used in the multiple chemical reactions such as hydrogenation, oxidation and dehydrogenation. Research shows,Copper-based catalysts has good methanol dehydrogenation activity. But, due to fusing point (1083 DEG C) and the Tammann of copperTemperature (405 DEG C) is lower, and in high-temperature roasting, reduction and course of reaction, copper nano particles very easily occursSintering. Sodesawa etc. have proposed a kind of ion-exchange and have prepared Cu-SiO2Catalyst, reacts at methanol dehydrogenationMiddle catalytic life only has 10h. Guerreiro etc. adopt the preparation Cu/SiO that uses the same method2Catalyst, obtainsThe nano copper particle of high degree of dispersion, but do not discuss its catalytic stability in detail. Thereby, prepare a kind of particleSize is little, decentralization is high, and the Nanometer Copper catalyst material of Heat stability is good to probe in detail its catalysis stableProperty has important learning value and realistic meaning.
Summary of the invention
The object of this invention is to provide the methanol dehydrogenation methyl formate copper processed base of a kind of good stability, long catalytic lifeCatalysts and its preparation method and application.
Catalyst of the present invention is a kind of constitutionally stable copper base nucleocapsid catalyst, by copper oxide nanometer particle and JieHole silica composition, wherein nano cupric oxide particle is wrapped in mesoporous silicon oxide shell. Cupric oxide containsAmount is 5wt%-70wt%, and particle size is less than 10nm, and decentralization reaches 5.0%-30.0%; Meso-porous titanium dioxideSilicone content is 30wt%-95wt%, and the average pore size of mesoporous silicon oxide shell holes is 2.0-5.0nm, thanSurface area is 100-1000m2/ g, shell thickness is 10-400nm; Nano copper oxide meso-porous silica coreShell microballoon is of a size of 200-1000nm.
The preparation method of catalyst of the present invention is as follows:
(1) adopt thermal decomposition method to prepare cupric oxide nano nuclear particle
Mantoquita is dissolved in alcoholic solution, and the mass volume ratio of controlling mantoquita and alcoholic solution is 1-10g/L, addsEnter dispersant, the mass volume ratio of dispersant and alcoholic solution is controlled at 5-25g/L, reaction at 160-200 DEG C1-5h, obtains copper oxide nanometer particle;
(2) adoptMethod parcel mesoporous silicon oxide shell
To add pore-foaming agent to add mother liquor, the mass volume ratio of controlling pore-foaming agent and mother liquor is 0.1-10g/L,Using aqueous slkali to regulate mother liquor pH value is 7-12, by whole the copper oxide nanometer particle obtaining in step (1)Join in above-mentioned mother liquor, then add alkyl silicate, control the quality volume of alkyl silicate and mother liquorThan for 0.5-10g/L, at 20-60 DEG C, react 6-72h, through filtration, Washing of Filter Cake, dry, roastingBurn, obtain nano copper oxide meso-porous silicon dixoide nucleocapsid structure material.
By changing the pH value of proportioning, pore-foaming agent addition and mother liquor of mother liquor, can control alkyl silicateHydrolysis rate, thereby regulate the pore structure of silica shell; By change alkyl silicate amount justThe thickness of adjustable shell.
As above the described mantoquita of step (1) is copper chloride, copper nitrate or Schweinfurt green.
As above the described alcoholic solution of step (1) is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or butanols.
As above the described dispersant of step (1) be softex kw, polyvinylpyrrolidone orPolyethylene glycol.
As above step (2) mother liquor is water and/or alcohol, and alcohol is methyl alcohol, ethanol, propyl alcohol, amylalcohol or hexanol.
As above the described pore-foaming agent of step (2) is DTAB, myristyl trimethyl bromineChange ammonium, softex kw or Cetyltrimethylammonium bromide.
As above the described aqueous slkali of step (2) be sodium hydroxide solution, potassium hydroxide solution, urea liquid,Ammonia spirit or sodium phenate solution.
As above the described alkyl silicate of step (2) is methyl silicate, ethyl orthosilicate or positive silicic acid propyl ester.
As above the described drying condition of step (2) is 40-150 DEG C of air/vacuum drying 8-24h, roasting barPart is 300-800 DEG C of static state/dynamic air roasting 2-24h.
The prepared catalyst of the present invention is for methanol dehydrogenation methyl formate fixed bed reactors processed. Operation barPart is: reducing condition is, H2Content is the H of 10%-50% (v/v)2/ Ar mixed atmosphere, 200-350 DEG C,Normal pressure, air speed is 5000-12000mLg-1·h-1, recovery time 5-24h. Reaction condition is, 180-250DEG C, normal pressure, mass space velocity is 1-8h-1(g/g)。
Reaction result is, methanol conversion 20%-50%, and the selective 70%-100% of methyl formate, catalysis is steadyQualitative good (250 DEG C of reactions can be stablized 100h).
Catalyst prepared by the present invention has following characteristics: copper oxide nanometer particle size little (being less than 10nm),Decentralization high (5.0%-30.0%), good stability (800 DEG C of roasting 10h); Silica shell hole is sent outReach (2.0-5.0nm is mesoporous), thickness is adjustable (10-400nm), is beneficial to the diffusion of reactant and product; ReceiveThe copper oxide meso-porous silica core-shell particle size of rice is even, size controlled (200-1000nm), dispersivenessGood. Nano cupric oxide particle size is little, prepares in methyl formate reaction at methanol dehydrogenation, and methanol conversion is20%-50%, methyl formate is selectively 70%-100%; Copper oxide nanometer particle decentralization is high, and has mesoporous twoThe protective effect of silica shell, methanol dehydrogenation prepare copper particle in methyl formate reaction can not assemble,Sintering, catalytic stability is good, the life-span long (250 DEG C of reactions can be stablized 100h).
Brief description of the drawings
The nano copper oxide meso-porous silica core-shell particle that Fig. 1 embodiment of the present invention 13 is prepared
The prepared nano copper oxide meso-porous silica of the known embodiment of the present invention 13 from accompanying drawing 1 (a)Nucleocapsid particles size uniform, good dispersion, microballoon size is about 700nm; From accompanying drawing 1 (b) knownThe nano copper oxide meso-porous silicon dixoide nucleocapsid structure material that inventive embodiments 13 is prepared, it is nano oxidizedShot copper footpath average-size be 3.8nm, decentralization up to 28.0%, and after roasting, there is not sintering at 800 DEG C,Its Heat stability is good is described; The prepared nano cupric oxide of the known embodiment of the present invention 13 from accompanying drawing 1 (c)Meso-porous silica core-shell structural material, its silica shell hole prosperity, average pore size 4.2nm, thanSurface area 854m2/g。
The prepared nano copper oxide meso-porous SiO 2 catalyst of Fig. 2 embodiment of the present invention 6 is in methanol dehydrogenation first processedCatalytic performance in the reaction of acid methyl esters
From accompanying drawing 2, the prepared nano copper oxide meso-porous silica core-shell of the known embodiment of the present invention 6 is urgedAgent, in methanol dehydrogenation methyl formate reaction processed, 230 DEG C of reactions can be stablized 100h, have good stabilityWith long advantage of life-span.
Detailed description of the invention
By the following examples the present invention is described in detail, but the present invention is not limited to these embodiment.
Embodiment 1
The preparation of nano cupric oxide particle: by first to 0.5g copper chloride and 2.5g softex kwAfter be dissolved in 500mL methanol solution, react 5h at 160 DEG C.
Being coated of silica shell: drip sodium hydroxide solution in 1000mL methanol solution, regulator solutionPH value is 12, and the nano cupric oxide particle of preparation is all joined in gained solution, dropwise adds 0.5 afterwardsG methyl silicate, reacts 6h at 60 DEG C. Through filtration, Washing of Filter Cake, 40 DEG C of dry 24h of air,After the processes such as 800 DEG C of still air roasting 2h, obtain nano copper oxide meso-porous silica core-shell particle. ItsMiddle cupric oxide content is 54wt%, and average particle size particle size is 8.4nm, and decentralization is 7.8%; Meso-porous titanium dioxideSilicone content is 46wt%, and mesoporous silicon oxide shell average pore size is 5.0nm, and specific area is 100m2/g，Shell thickness is about 10nm; Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 200nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.3g20-40 object, at 50%H2/Ar(v/v)Atmosphere Program heating reduction. Reducing condition is, 350 DEG C, and normal pressure, volume space velocity 6000mLg-1·h-1，Recovery time 5h. Reaction condition is, 180 DEG C, and normal pressure, mass space velocity is 1h-1(g/g). Methanol conversionRate 25%, methyl formate is selective 95%, and catalytic life can reach 180h.
Embodiment 2
The preparation of nano cupric oxide particle: 1g copper nitrate and 5g polyvinylpyrrolidone are successively dissolved inIn 500mL ethanolic solution, react 4h at 170 DEG C.
Silica shell coated: after 100mL water and 900mL ethanol are mixed, add wherein1g DTAB, dripping potassium hydroxide solution regulator solution pH value is 11.5, will prepareNano cupric oxide particle all join in gained solution, dropwise add afterwards 1g ethyl orthosilicate, 50 DEG CLower reaction 6h. Through filtration, Washing of Filter Cake, 60 DEG C of vacuum drying 20h, 300 DEG C of dynamic air roastingsAfter the processes such as 24h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 50Wt%, average particle size particle size is 8.0nm, decentralization is 6.5%; Meso-porous titanium dioxide silicone content is 50wt%,Mesoporous silicon oxide shell average pore size is 2.0nm, and specific area is 158m2/ g, shell thickness is about 22Nm; Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 270nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.15g20-40 object, at 40%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 300 DEG C, and normal pressure, volume space velocity 8000mL·g-1·h-1, recovery time 10h. Reaction condition is, 190 DEG C, and normal pressure, mass space velocity is 2h-1(g/g)。Methanol conversion 26%, methyl formate is selective 91%, and catalytic life can reach 180h.
Embodiment 3
The preparation of nano cupric oxide particle: 1.5g Schweinfurt green and 3g polyethylene glycol are successively dissolved in to 500mLIn ethanolic solution, react 3h at 180 DEG C.
Silica shell coated: after 200mL water and 800mL propyl alcohol are mixed, add wherein2g TTAB, dripping ammonia spirit regulator solution pH value is 11, by the nanometer of preparationCopper oxide particle all joins in gained solution, dropwise adds afterwards the positive silicic acid propyl ester of 1.5g, at 40 DEG CReaction 12h. Through filtration, Washing of Filter Cake, 80 DEG C of dry 20h of air, 500 DEG C of dynamic air roastingsAfter the processes such as 12h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 58wt%,Average particle size particle size is 9.2nm, and decentralization is 6.2%; Meso-porous titanium dioxide silicone content is 42wt%, mesoporous twoSilica shell average pore size is 2.8nm, and specific area is 302m2/ g, shell thickness is about 40nm;Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 300nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.1g20-40 object, at 30%H2/Ar(v/v)Atmosphere Program heating reduction. Reducing condition is, 250 DEG C, and normal pressure, volume space velocity 9000mLg-1·h-1，Recovery time 15h. Reaction condition is, 200 DEG C, and normal pressure, mass space velocity is 3h-1(g/g). Methyl alcohol turnsRate 30%, methyl formate is selective 92%, and catalytic life can reach 180h.
Embodiment 4
The preparation of nano cupric oxide particle: by successively molten to 2g copper chloride and 5g softex kwSolution, in 500mL ethanolic solution, is reacted 2h at 190 DEG C.
Silica shell coated: after 300mL water and 700mL amylalcohol are mixed, add wherein3g softex kw, dripping urea liquid regulator solution pH value is 10.5, by receiving of preparationRice copper oxide particle all joins in gained solution, dropwise adds afterwards 4g methyl silicate, at 30 DEG CReaction 24h. Through filtration, Washing of Filter Cake, 100 DEG C of dry 16h of air, 600 DEG C of still air roastingsAfter the processes such as 10h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 36wt%,Average particle size particle size is 6.8nm, and decentralization is 11.0%; Meso-porous titanium dioxide silicone content is 64wt%, mesoporousSilica shell average pore size is 3.3nm, and specific area is 395m2/ g, shell thickness is about 80nm;Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 450nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.075g20-40 object, at 20%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 200 DEG C, and normal pressure, volume space velocity 10000mL·g-1·h-1, recovery time 24h. Reaction condition is, 210 DEG C, and normal pressure, mass space velocity is 4h-1(g/g)。Methanol conversion 28%, methyl formate is selective 90%, and catalytic life can reach 150h.
Embodiment 5
The preparation of nano cupric oxide particle: 2.5g copper nitrate and 7.5g polyvinylpyrrolidone are successively dissolvedIn 500mL ethanolic solution, react 1h at 200 DEG C.
Silica shell coated: after 400mL water and 600mL hexanol are mixed, add wherein4g Cetyltrimethylammonium bromide, dripping sodium phenate solution regulator solution pH value is 10, by receiving of preparationRice copper oxide particle all joins in gained solution, dropwise adds afterwards 10g ethyl orthosilicate, 20 DEG CLower reaction 72h. Through filtration, Washing of Filter Cake, 120 DEG C of dry 12h of air, 400 DEG C of dynamic air roastingsAfter burning the processes such as 20h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 22Wt%, average particle size particle size is 4.7nm, decentralization is 21.0%; Meso-porous titanium dioxide silicone content is 78wt%,Mesoporous silicon oxide shell average pore size is 4.7nm, and specific area is 279m2/ g, shell thickness is about 300Nm; Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 800nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.06g20-40 object, at 10%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 250 DEG C, and normal pressure, volume space velocity 12000mL·g-1·h-1, recovery time 20h. Reaction condition is, 220 DEG C, and normal pressure, mass space velocity is 5h-1(g/g)。Methanol conversion 32%, methyl formate is selective 87%, and catalytic life can reach 168h.
Embodiment 6
The preparation of nano cupric oxide particle: 3g Schweinfurt green and 12g polyethylene glycol are successively dissolved in to 500mLIn ethanolic solution, react 2h at 200 DEG C.
Silica shell coated: after 500mL water and 500mL methyl alcohol are mixed, add wherein5g DTAB, dripping sodium hydroxide solution regulator solution pH value is 9.5, will prepareNano cupric oxide particle all join in gained solution, dropwise add afterwards the positive silicic acid propyl ester of 3g, 35 DEG CLower reaction 36h. Through filtration, Washing of Filter Cake, 150 DEG C of vacuum drying 8h, 700 DEG C of dynamic air roastingsAfter burning the processes such as 8h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 55Wt%, average particle size particle size is 8.7nm, decentralization is 7.0%; Meso-porous titanium dioxide silicone content is 45wt%,Mesoporous silicon oxide shell average pore size is 2.5nm, and specific area is 721m2/ g, shell thickness is about 60Nm; Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 380nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.05g20-40 object, at 20%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 300 DEG C, and normal pressure, volume space velocity 10000mL·g-1·h-1, recovery time 10h. Reaction condition is, 230 DEG C, and normal pressure, mass space velocity is 6h-1(g/g)。Methanol conversion 40%, methyl formate is selective 85%, and catalytic life can reach 100h. As shown in Figure 2, urgeAgent is after reaction 100h, and it is stable that activity still keeps, and illustrates that its chemical stability is good, long catalytic life.
Embodiment 7
The preparation of nano cupric oxide particle: by successively molten to 4g copper chloride and 4g softex kwSolution, in 500mL ethanolic solution, is reacted 4h at 200 DEG C.
Silica shell coated: after 600mL water and 400mL ethanol are mixed, add wherein6g TTAB, dripping potassium hydroxide solution regulator solution pH value is 9, by what prepareNano cupric oxide particle all joins in gained solution, dropwise adds afterwards 9g methyl silicate, 25 DEG CLower reaction 48h. Through filtration, Washing of Filter Cake, 40 DEG C of vacuum drying 22h, 350 DEG C of static roasting 24hMust nano copper oxide meso-porous silica core-shell particle etc. after process. Wherein cupric oxide content is 30wt%, flatAll particle size is 6.2nm, and decentralization is 15.0%; Meso-porous titanium dioxide silicone content is 70wt%, mesoporous twoSilica shell average pore size is 3.4nm, and specific area is 894m2/ g, shell thickness is about 240nm;Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 650nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.043g20-40 object, at 30%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 350 DEG C, and normal pressure, volume space velocity 8000mL·g-1·h-1, recovery time 5h. Reaction condition is, 240 DEG C, and normal pressure, mass space velocity is 7h-1(g/g)。Methanol conversion 35%, methyl formate is selective 80%, and catalytic life can reach 120h.
Embodiment 8
The preparation of nano cupric oxide particle: 5g copper nitrate and 12.5g polyvinylpyrrolidone are successively dissolvedIn 500mL ethanolic solution, react 5h at 200 DEG C.
Silica shell coated: after 700mL water and 300mL propyl alcohol are mixed, add wherein7g softex kw, dripping ammonia spirit regulator solution pH value is 8.5, by receiving of preparationRice copper oxide particle all joins in gained solution, dropwise adds afterwards 10g ethyl orthosilicate, 45 DEG CLower reaction 72h. Through filtration, Washing of Filter Cake, 60 DEG C of dry 20h of air, 550 DEG C of still air roastingsAfter burning the processes such as 16h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 28Wt%, average particle size particle size is 5.3nm, decentralization is 18.0%; Meso-porous titanium dioxide silicone content is 72wt%,Mesoporous silicon oxide shell average pore size is 3.3nm, and specific area is 915m2/ g, shell thickness is about 400Nm; Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 1000nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.0375g20-40 object, at 40%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 300 DEG C, and normal pressure, volume space velocity 6000mL·g-1·h-1, recovery time 10h. Reaction condition is, 250 DEG C, and normal pressure, mass space velocity is 8h-1(g/g)。Methanol conversion 50%, methyl formate is selective 70%, and catalytic life can reach 100h.
Embodiment 9
The preparation of nano cupric oxide particle: 5g Schweinfurt green and 2.5g polyethylene glycol are successively dissolved in to 500mLIn ethanolic solution, react 5h at 190 DEG C.
Silica shell coated: after 800mL water and 200mL amylalcohol are mixed, add wherein8g Cetyltrimethylammonium bromide, dripping urea liquid regulator solution pH value is 8, by the nanometer of preparationCopper oxide particle all joins in gained solution, dropwise adds afterwards the positive silicic acid propyl ester of 1g, anti-at 55 DEG CAnswer 6h. Through filtration, Washing of Filter Cake, 80 DEG C of vacuum drying 16h, 300 DEG C of dynamic air roasting 4hMust nano copper oxide meso-porous silica core-shell particle etc. after process. Wherein cupric oxide content is 70wt%, flatAll particle size is 10nm, and decentralization is 5.0%; Meso-porous titanium dioxide silicone content is 30wt%, mesoporous dioxySiClx shell average pore size is 4.5nm, and specific area is 748m2/ g, shell thickness is about 15nm; OxygenChanging copper mesoporous silicon dioxide micro-sphere average grain diameter is 285nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.043g20-40 object, at 50%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 250 DEG C, and normal pressure, volume space velocity 6000mL·g-1·h-1, recovery time 15h. Reaction condition is, 230 DEG C, and normal pressure, mass space velocity is 7h-1(g/g)。Methanol conversion 33%, methyl formate is selective 89%, and catalytic life can reach 100h.
Embodiment 10
The preparation of nano cupric oxide particle: by successively molten to 4g copper chloride and 6g softex kwSolution, in 500mL ethanolic solution, is reacted 4h at 190 DEG C.
Silica shell coated: after 900mL water and 100mL hexanol are mixed, add wherein9g DTAB, dripping sodium phenate solution regulator solution pH value is 7.5, by what prepareNano cupric oxide particle all joins in gained solution, dropwise adds afterwards 5g methyl silicate, 40 DEG CLower reaction 24h. Through filtration, Washing of Filter Cake, 100 DEG C of vacuum drying 10h, 450 DEG C of still air roastingsAfter burning the processes such as 18h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 44Wt%, average particle size particle size is 7.1nm, decentralization is 8.0%; Meso-porous titanium dioxide silicone content is 56wt%,Mesoporous silicon oxide shell average pore size is 2.7nm, and specific area is 659m2/ g, shell thickness is about 75Nm; Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 380nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.05g20-40 object, at 40%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 200 DEG C, and normal pressure, volume space velocity 8000mL·g-1·h-1, recovery time 20h. Reaction condition is, 210 DEG C, and normal pressure, mass space velocity is 6h-1(g/g)。Methanol conversion 30%, methyl formate is selective 86%, and catalytic life can reach 120h.
Embodiment 11
The preparation of nano cupric oxide particle: 3g copper nitrate and 10.5g polyvinylpyrrolidone are successively dissolvedIn 500mL ethanolic solution, react 4h at 180 DEG C.
Being coated of silica shell: in 1000mL water, add 10g TTAB,Dripping sodium hydroxide solution regulator solution pH value is 7, and the nano cupric oxide particle of preparation is all joined to instituteIn solution, dropwise add afterwards 8g ethyl orthosilicate, react 48h at 60 DEG C. Through filtration, filter cakeAfter the processes such as washing, 120 DEG C of vacuum drying 8h, 650 DEG C of dynamic air roasting 10h, obtain nano cupric oxideMeso-porous silica core-shell particle. Wherein cupric oxide content is 30wt%, and average particle size particle size is 6.0nm,Decentralization is 14.0%; Meso-porous titanium dioxide silicone content is 70wt%, and mesoporous silicon oxide shell average pore size is3.0nm, specific area is 1000m2/ g, shell thickness is about 210nm; Copper oxide meso-porous silicaMicrosphere average grain diameter is 620nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.06g20-40 object, at 30%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 250 DEG C, and normal pressure, volume space velocity 8000mL·g-1·h-1, recovery time 20h. Reaction condition is, 190 DEG C, and normal pressure, mass space velocity is 5h-1(g/g)。Methanol conversion 23%, methyl formate is selective 98%, and catalytic life can reach 180h.
Embodiment 12
The preparation of nano cupric oxide particle: 2g Schweinfurt green and 12g polyethylene glycol are successively dissolved in to 500mLIn ethanolic solution, react 5h at 180 DEG C.
Silica shell coated: after 900mL water and 100mL methyl alcohol are mixed, add wherein4g softex kw, dripping potassium hydroxide solution regulator solution pH value is 8, by what prepareNano cupric oxide particle all joins in gained solution, dropwise adds afterwards the positive silicic acid propyl ester of 2g, 50 DEG CLower reaction 12h. Through filtration, Washing of Filter Cake, 150 DEG C of dry 12h of air, 350 DEG C of dynamic air roastingsAfter burning the processes such as 4h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 52Wt%, average particle size particle size is 8.0nm, decentralization is 7.8%; Meso-porous titanium dioxide silicone content is 48wt%,Mesoporous silicon oxide shell average pore size is 3.7nm, and specific area is 542m2/ g, shell thickness is about 30Nm; Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 360nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.075g20-40 object, at 20%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 300 DEG C, and normal pressure, volume space velocity 12000mL·g-1·h-1, recovery time 24h. Reaction condition is, 180 DEG C, and normal pressure, mass space velocity is 4h-1(g/g)。Methanol conversion 20%, methyl formate is selective 100%, and catalytic life can reach 180h.
Embodiment 13
The preparation of nano cupric oxide particle: by successively molten to 1g copper chloride and 7g softex kwSolution, in 500mL ethanolic solution, is reacted 5h at 170 DEG C.
Silica shell coated: after 600mL water and 400mL methyl alcohol are mixed, add wherein6g Cetyltrimethylammonium bromide, dripping ammonia spirit regulator solution pH value is 9, by the nanometer of preparationCopper oxide particle all joins in gained solution, dropwise adds afterwards 6g methyl silicate, anti-at 40 DEG CAnswer 36h. Through filtration, Washing of Filter Cake, 120 DEG C of dry 12h of air, 800 DEG C of dynamic air roastings 10After the processes such as h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 16wt%,Average particle size particle size is 3.8nm, and decentralization is 28.0%; Meso-porous titanium dioxide silicone content is 84wt%, mesoporousSilica shell average pore size is 4.2nm, and specific area is 854m2/ g, shell thickness is about 200nm;Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 700nm. As shown in Figure 1, the nano cupric oxide of preparationMeso-porous silica core-shell particle size is even, good dispersion; Copper oxide nanometer particle average-size is 3.8Nm, decentralization are high, and after roasting, sintering do not occur at 800 DEG C, and its Heat stability is good is described; SilicaThe prosperity of shell hole.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.1g20-40 object, at 10%H2/Ar(v/v)Atmosphere Program heating reduction. Reducing condition is, 350 DEG C, and normal pressure, volume space velocity 10000mLg-1·h-1，Recovery time 10h. Reaction condition is, 200 DEG C, and normal pressure, mass space velocity is 3h-1(g/g). Methyl alcohol turnsRate 22%, methyl formate is selective 88%, and catalytic life can reach 180h.
Embodiment 14
The preparation of nano cupric oxide particle: 0.5g copper nitrate and 4g polyvinylpyrrolidone are successively dissolved inIn 500mL ethanolic solution, react 3h at 160 DEG C.
Silica shell coated: after 300mL water and 700mL ethanol are mixed, add wherein3.5g DTAB, dripping urea liquid regulator solution pH value is 10, by receiving of preparationRice copper oxide particle all joins in gained solution, dropwise adds afterwards 7g ethyl orthosilicate, at 30 DEG CReaction 48h. Through filtration, Washing of Filter Cake, 100 DEG C of dry 24h of air, 750 DEG C of dynamic air roastingsAfter the processes such as 12h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 5wt%,Average particle size particle size is 3.0nm, and decentralization is 30.0%; Meso-porous titanium dioxide silicone content is 95wt%, mesoporousSilica shell average pore size is 2.4nm, and specific area is 298m2/ g, shell thickness is about 400nm;Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 900nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.15g20-40 object, at 50%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 300 DEG C, and normal pressure, volume space velocity 8000mL·g-1·h-1, recovery time 15h. Reaction condition is, 220 DEG C, and normal pressure, mass space velocity is 2h-1(g/g)。Methanol conversion 48%, methyl formate is selective 76%, and catalytic life can reach 120h.
Embodiment 15
The preparation of nano cupric oxide particle: 3.5g Schweinfurt green and 10.5g polyethylene glycol are successively dissolved in to 500In mL ethanolic solution, react 2h at 170 DEG C.
Silica shell coated: after 100mL water and 900mL propyl alcohol are mixed, add wherein7g TTAB, dripping sodium phenate solution regulator solution pH value is 11, by receiving of preparationRice copper oxide particle all joins in gained solution, dropwise adds afterwards the positive silicic acid propyl ester of 3.5g, 20 DEG CLower reaction 72h. Through filtration, Washing of Filter Cake, 80 DEG C of vacuum drying 12h, 400 DEG C of still air roastingsAfter burning the processes such as 2h, obtain nano copper oxide meso-porous silica core-shell particle. Wherein cupric oxide content is 60Wt%, average particle size particle size is 9.6nm, decentralization is 5.8%; Meso-porous titanium dioxide silicone content is 40wt%,Mesoporous silicon oxide shell average pore size is 3.1nm, and specific area is 884m2/ g, shell thickness is about 50Nm; Copper oxide meso-porous silicon dioxide microsphere average grain diameter is 400nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.3g20-40 object, at 40%H2/Ar(v/v)Atmosphere Program heating reduction. Reducing condition is, 250 DEG C, and normal pressure, volume space velocity 6000mLg-1·h-1，Recovery time 20h. Reaction condition is, 240 DEG C, and normal pressure, mass space velocity is 1h-1(g/g). Methyl alcohol turnsRate 42%, methyl formate is selective 79%, and catalytic life can reach 100h.
Embodiment 16
The preparation of nano cupric oxide particle: by 4.5g copper chloride and 9g softex kw priorityBe dissolved in 500mL ethanolic solution, react 1h at 180 DEG C.
Being coated of silica shell: will in 1000mL amylalcohol, add 4.5g softex kw,Dripping sodium hydroxide solution regulator solution pH value is 12, and the nano cupric oxide particle of preparation is all joined to instituteIn solution, dropwise add afterwards 9g methyl silicate, react 60h at 40 DEG C. Through filtration, filter cakeAfter the processes such as washing, 60 DEG C of vacuum drying 20h, 500 DEG C of dynamic air roasting 4h, obtain nano cupric oxideMeso-porous silica core-shell particle. Wherein cupric oxide content is 37wt%, and average particle size particle size is 6.5nm,Decentralization is 11.0%; Meso-porous titanium dioxide silicone content is 63wt%, and mesoporous silicon oxide shell average pore size is3.6nm, specific area is 652m2/ g, shell thickness is about 350nm; Copper oxide meso-porous silica is micro-Ball average grain diameter is 880nm.
In atmospheric fixed bed reactor, load the above-mentioned catalyst of 0.075g20-40 object, at 10%H2/Ar(v/v) atmosphere Program heating reduction. Reducing condition is, 300 DEG C, and normal pressure, volume space velocity 8000mL·g-1·h-1, recovery time 10h. Reaction condition is, 220 DEG C, and normal pressure, mass space velocity is 4h-1(g/g)。Methanol conversion 38%, methyl formate is selective 84%, and catalytic life can reach 150h.
Claims (12)
1. for a copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed, it is characterized in that catalyst is made up of copper oxide nanometer particle and mesoporous silicon oxide, wherein nano cupric oxide particle is wrapped in mesoporous silicon oxide shell; Cupric oxide content is 5wt%-70wt%, and particle size is less than 10nm, and decentralization reaches 5.0%-30.0%; Meso-porous titanium dioxide silicone content is 30wt%-95wt%, and the average pore size of mesoporous silicon oxide shell holes is 2.0-5.0nm, and specific area is 100-1000m2/ g, shell thickness is 10-400nm; Nano copper oxide meso-porous silica core-shell microspheres is of a size of 200-1000nm.
2. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 1, is characterized in that comprising the steps:
(1) prepare cupric oxide nano nuclear particle
Mantoquita is dissolved in alcoholic solution, and the mass volume ratio of controlling mantoquita and alcoholic solution is 1-10g/L, adds dispersant, and the mass volume ratio of dispersant and alcoholic solution is controlled at 5-25g/L, 160-200oUnder C, react 1-5h, obtain copper oxide nanometer particle;
(2) parcel mesoporous silicon oxide shell
To add pore-foaming agent mother liquor, the mass volume ratio of controlling pore-foaming agent and mother liquor is 0.1-10g/L, using aqueous slkali to regulate mother liquor pH value is 7-12, the copper oxide nanometer particle obtaining in step (1) is all joined in above-mentioned mother liquor, then add alkyl silicate, the mass volume ratio of controlling alkyl silicate and mother liquor is 0.5-10g/L, at 20-60oUnder C, react 6-72h, through filtration, Washing of Filter Cake, dry, roasting, obtain nano copper oxide meso-porous silicon dixoide nucleocapsid structure material.
3. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 2, is characterized in that the described mantoquita of step (1) is copper chloride, copper nitrate or Schweinfurt green.
4. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 2, is characterized in that the described alcoholic solution of step (1) is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or butanols.
5. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 2, is characterized in that the described dispersant of step (1) is softex kw, polyvinylpyrrolidone or polyethylene glycol.
6. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 2, is characterized in that step (2) mother liquor is water and/or alcohol.
7. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 6, is characterized in that described alcohol is methyl alcohol, ethanol, propyl alcohol, amylalcohol or hexanol.
8. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 2, is characterized in that the described pore-foaming agent of step (2) is DTAB, TTAB, softex kw or Cetyltrimethylammonium bromide.
9. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 2, is characterized in that the described aqueous slkali of step (2) is sodium hydroxide solution, potassium hydroxide solution, urea liquid, ammonia spirit or sodium phenate solution.
10. the preparation method of a kind of copper base nucleocapsid catalyst for methanol dehydrogenation methyl formate processed as claimed in claim 2, is characterized in that the described alkyl silicate of step (2) is methyl silicate, ethyl orthosilicate or positive silicic acid propyl ester.
The preparation method of 11. a kind of copper base nucleocapsid catalysts for methanol dehydrogenation methyl formate processed as claimed in claim 2, is characterized in that the described drying condition of step (2) is 40-150oC air or vacuum drying 8-24h, roasting condition is 300-800oC static state or dynamic air roasting 2-24h.
The application of 12. a kind of copper base nucleocapsid catalysts for methanol dehydrogenation methyl formate processed as claimed in claim 1, is characterized in that comprising the steps:
Catalyst is for methanol dehydrogenation methyl formate fixed bed reactors processed, and reducing condition is, H2Volume content is the H of 10%-50%2/ Ar mixed atmosphere, 200-350oC, normal pressure, air speed is 5000-12000mLg-1·h-1, recovery time 5-24h; Reaction condition is, 180-250oC, normal pressure, mass space velocity is 1-8h-1。
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| CN114761520A (en) * | 2019-09-26 | 2022-07-15 | 阿布扎比国家石油公司 | For removing H from gas streams2Yolk-shell nanoparticles of S |
| CN115672322A (en) * | 2022-10-12 | 2023-02-03 | 中国石油大学(华东) | Cu-series eggshell catalyst, preparation method and oxalic acid diester hydrogenation method |
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