CN109529874A - A kind of mesoporous silicon oxide clad type Mock gold catalyst and preparation method thereof - Google Patents
A kind of mesoporous silicon oxide clad type Mock gold catalyst and preparation method thereof Download PDFInfo
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- CN109529874A CN109529874A CN201811410727.1A CN201811410727A CN109529874A CN 109529874 A CN109529874 A CN 109529874A CN 201811410727 A CN201811410727 A CN 201811410727A CN 109529874 A CN109529874 A CN 109529874A
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- CN
- China
- Prior art keywords
- mock gold
- silicon oxide
- clad type
- catalyst
- mesoporous silicon
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 67
- 239000010931 gold Substances 0.000 title claims abstract description 67
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001666 catalytic steam reforming of ethanol Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 25
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 239000013049 sediment Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 8
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical group [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 238000001507 sample dispersion Methods 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000013335 mesoporous material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229960004756 ethanol Drugs 0.000 description 22
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000011549 crystallization solution Substances 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WBUZNMHGYZJJTL-UHFFFAOYSA-N ethanol;gold Chemical compound [Au].CCO WBUZNMHGYZJJTL-UHFFFAOYSA-N 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B01J35/398—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1229—Ethanol
Abstract
The present invention relates to catalyst for preparing hydrogen field, specifically a kind of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst and preparation method thereof.It is by nuclear phase Mock gold structure and shell mesoporous silicon oxide structure composition.Catalytic active site is wrapped in mesoporous material by the present invention in the form of alloy.Improve catalytic perfomance, in terms of play an important role.Main reason is that alloy plays synergistic effect in ethanol steam reforming reaction between being more advantageous to bimetallic, the content of by-product is reduced, carbon distribution is reduced；Shell can be good at playing the role of stablizing and protecting catalytic active component；Catalyst with this structure can effectively avoid the migration and reunion between active component；The meso-hole structure of shell can be conducive to effective diffusion of reaction molecular and product molecule.Final activity, selectivity and the stability for improving ethanol steam reforming catalysts.
Description
Technical field
The present invention relates to catalyst for preparing hydrogen field, specifically a kind of mesoporous silicon oxide clad type Mock gold ethanol water is steamed
Gas reforming hydrogen-production catalyst and preparation method thereof.
Background technique
Three kinds of petroleum, coal and natural gas fossil class A fuel As are still the current most important energy consumption resource in the whole world, tradition
The use degree of the energy rises year by year, and faces the cruel reality of lack of energy and environmental pollution.Hydrogen Energy is known as being most to manage 21 century
The clean energy resource thought, with the incomparable advantage of other energy.Wherein wood-based composites vapor reforming hydrogen production, there is no pair
The dependence of traditional fossil energy possesses the advantages such as nontoxic, easy storage and transportation, unit energy height, hydrogen content height and becomes and pay close attention in recent years
Hot spot.
The catalytic active site of hydrogen production by ethanol steam reforming catalyst mainly passes through infusion process at present, coprecipitation and heavy
The product precipitation method are supported on carrier surface, due to little metallic particles surface energy with higher, the Yi Fasheng in catalytic reaction process
Migration, reunion, sintering form big metallic particles, reduce the active sites contact surface of catalyst, and catalytic performance significantly reduces, makes to urge
The stability of agent can not meet industrial demand.
Summary of the invention
The purpose of the present invention is being directed to the state and deficiency of background technique, provide that a kind of synthesis step is simple, easy control of structure
The preparation method of the mesoporous silicon oxide clad type Mock gold catalyst of system, high-purity.
The present invention is achieved by the following technical solutions: a kind of mesoporous silicon oxide clad type Mock gold ethanol water steaming
Gas reforming hydrogen-production catalyst is by nuclear phase Mock gold structure and shell mesoporous silicon oxide structure composition.
Catalytic active site is wrapped in mesoporous material by the present invention in the form of alloy.Improving catalytic perfomance, knot
Structure stability etc. plays an important role.Main reason is that alloy is more advantageous between bimetallic in ethanol steam reforming
Synergistic effect is played in reaction, reduces the content of by-product, reduces carbon distribution；Shell, which can be good at playing, stablizes and protects catalysis
The effect of active component；Catalyst with this structure can effectively avoid the migration and reunion between active component；Shell
Meso-hole structure can be conducive to effective diffusion of reaction molecular and product molecule.Final raising ethanol steam reforming reaction is urged
Activity, selectivity and the stability of agent.
As the further improvement of technical solution of the present invention, the content of the nuclear phase Mock gold structure is 5 ~ 20wt%, institute
The content for stating shell meso-porous titanium dioxide silicon structure is 80 ~ 95wt%.
As the further improvement of technical solution of the present invention, the crystal particle diameter of the catalyst is 150 ~ 350nm, and shell is situated between
Hole silicon dioxide structure with a thickness of 50 ~ 200nm.
Illustrate the present invention in order to clearer, the present invention provides a kind of mesoporous silicon oxide clad type Mock gold ethyl alcohol
The preparation method of vapor reforming hydrogen production catalyst, includes the following steps:
1) nuclear phase Mock gold powder is prepared
2) mesoporous silica clad type Mock gold material is prepared
According to nuclear phase Mock gold powder: deionized water: cetyl trimethylammonium bromide: ammonia spirit: ethyl orthosilicate=
0.01 ~ 0.1:10 ~ 15:0.03 ~ 0.2；The quality proportioning of 0.5 ~ 1.5:0.6 ~ 2.5；First disperse nuclear phase Mock gold powder in
In deionized water, 30min is stirred at 25 DEG C；Cetyl trimethylammonium bromide is dissolved in solution again, 3 ~ 5h is stirred at 25 DEG C；
Ammonia spirit is added in solution again, stirs 10min at 25 DEG C；Finally ethyl orthosilicate is added dropwise in solution, stirs 2h；
Gel after reaction is fitted into centrifuge tube and is centrifugated and washs, the revolution of centrifuge separation is 6000r/min, disengaging time
15min；Solid sediment is placed on filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree
10pa obtains mesoporous silica clad type Mock gold material after dry；
3) mesoporous silicon oxide clad type Mock gold catalyst is prepared
According to mesoporous silica clad type Mock gold material: ethyl alcohol: ammonium nitrate=0.1 ~ 0.3:250 ~ 500:1 ~ 3 quality
Proportion；At 60 DEG C, ammonium nitrate is dissolved in ethyl alcohol, after stirring 30min；In a nitrogen atmosphere, by sample dispersion in solution,
In 60 DEG C of 4 ~ 6h of condensing reflux；Sample after reflux is centrifuged, the revolution of centrifuge separation is 6000r/min, separation
Time 15min；Solid sediment is placed on filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree
Mesoporous silicon oxide clad type Mock gold catalyst can be obtained after dry in 10pa.
As the further improvement of preparation method technical solution of the present invention, the step 1) prepares nuclear phase Mock gold powder
The step of are as follows:
According to deionized water: polyvinylpyrrolidone: amino acids: soluble platinum source: soluble copper source=1 × 103~8
×103: 15 ~ 60:20 ~ 50:0.9 ~ 17.6:0.9 ~ 10 quality proportioning；First polyvinylpyrrolidone is dissolved in deionized water,
30min is stirred at room temperature, after ultrasonic 10min；Amino acids are added into mixed solution again, 10min is stirred at room temperature；Again
Soluble platinum source and soluble copper source are added into mixed solution, stirs 30min at room temperature；Mixed solution loading is had later
In the stainless steel cauldron of polytetrafluoroethyllining lining, the static reaction 3-6h under 180 ~ 200 DEG C of insulating boxs: after reaction, take
Reaction kettle is placed in quenching slot out, and 20 DEG C are quickly cooled in 10 DEG C of deionized water；Reaction kettle is opened, polytetrafluoroethyl-ne is taken out
Reaction product in polytetrafluoroethylcontainer container is placed in centrifuge tube by alkene container, is centrifuged and is washed, centrifuge separation
Revolution is 10000r/min, disengaging time 15min；Solid sediment is placed in evaporating dish, it is dry to be subsequently placed in vacuum oven
Dry, drying temperature is 50 DEG C, vacuum degree 10Pa, drying time 10h, obtains nuclear phase Mock gold powder after dry.
As the further improvement of preparation method technical solution of the present invention, soluble platinum source described in step 1) is six
It is hydrated chloroplatinic acid or platinum tetrachloride；Soluble copper source described in step 1) is copper nitrate or copper chloride.
After the mesoporous silicon oxide clad type Mock gold catalyst grinding that the present invention is prepared, it is pressed into 20 ~ 40 purposes
Particle.Using dehydrated alcohol and deionized water as raw material, using above-mentioned mesoporous silicon oxide clad type Mock gold catalyst, normal
Pressure, 250 DEG C ~ 400 DEG C of operation temperature, 0.1 ~ 5h of liquid phase feed air speed-1Under the conditions of carry out, reaction is converted into production based on hydrogen
Object.
Advantage of the invention is that alloy plays collaboration work between being more advantageous to bimetallic in ethanol steam reforming reaction
With reducing the content of by-product, reduce carbon distribution；Stabilization and protection of the mesoporous silicon oxide shell to catalytic active site, shell
Meso-hole structure can be conducive to reaction molecular and product molecule is effectively spread.Hydrogen yield and the service life for improving catalyst,
Catalysis aspect shows higher ethanol conversion and hydrogen selective, and the by-products such as methane, carbon monoxide, acetaldehyde significantly drop
It is low.The catalyst product purity prepared using preparation method of the present invention can reach 99.9%.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the TEM figure that embodiment 1 prepares Mock gold sample.
Fig. 2 is the XRD spectra that embodiment 1 prepares mesoporous silicon oxide clad type Mock gold catalyst.
Fig. 3 is the small angle XRD spectra that embodiment 1 prepares mesoporous silicon oxide clad type Mock gold catalyst.
Fig. 4 is the TEM figure that embodiment 1 prepares mesoporous silicon oxide clad type Mock gold catalyst.
Fig. 5 is nitrogen adsorption-desorption spectrogram that embodiment 2 prepares sample.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Technical solution of the present invention is described in detail with reference to the accompanying drawing.
Embodiment 1
A kind of preparation method of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, including it is as follows
Step:
1) polyvinylpyrrolidone (molecular weight is 30000) 0.04g is dissolved in 2mL deionized water, stirs 30min at room temperature,
After ultrasonic 10min；0.02g glycine is added into mixed solution again, 10min is stirred at room temperature；1mL is added into mixed solution again
Six hydrations chloroplatinic acid aqueous solution (30mM) and 1mL copper nitrate aqueous solution (30mM), stir 30min at room temperature；It later will mixing
Solution is fitted into the stainless steel cauldron with polytetrafluoroethyllining lining, the static reaction 6h under 200 DEG C of insulating boxs: reaction terminates
Afterwards, it takes out reaction kettle to be placed in quenching slot, 20 DEG C is quickly cooled in 10 DEG C of deionized water；Reaction kettle is opened, is taken out poly-
Crystallization solution in polytetrafluoroethylcontainer container is placed in centrifuge tube by tetrafluoroethene container, is centrifuged and is washed, centrifugation
Isolated revolution is 10000r/min, disengaging time 15min；Solid sediment is placed in evaporating dish, it is dry to be subsequently placed in vacuum
Dry case is dry, and drying temperature is 50 DEG C.
2) it first disperses 0.01g Mock gold powder in 10mL deionized water, stirs 30min at 25 DEG C；Again by 0.08g
Cetyl trimethylammonium bromide is dissolved in solution, stirs 4h at 25 DEG C；1mL ammonia spirit (25wt%, 0.91g/mL) is added again
Enter in solution, stirs 10min at 25 DEG C；It takes ethyl orthosilicate (0.93g/mL) 1.2mL to be slowly added dropwise, stirs 2h；After reacting
Gel be fitted into centrifuge tube and be centrifugated and wash, the revolution of centrifuge separation is 6000r/min, disengaging time 15min；It will consolidate
Body sediment is placed on filter paper, and in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.After drying
To mesoporous silica clad type Mock gold catalyst.
3) 2.395g ammonium nitrate is dissolved in 350mL ethyl alcohol (97wt%) at 60 DEG C, after stirring 30min；In nitrogen atmosphere
Under, it disperses 0.2g mesoporous silica clad type Mock gold catalyst in solution, in 60 DEG C of condensing reflux 4h；It will reflux
Sample afterwards is centrifuged, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；Solid sediment is placed in
On filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.Meso-porous titanium dioxide is obtained after drying
Silicon clad type Mock gold catalyst sample 1.
Ethanol steam weight is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Whole reaction evaluating.By the tabletting of mesoporous silicon oxide clad type Mock gold catalyst, it is crushed, is sized to 20 ~ 40 mesh, loadings
0.5g.Reaction is in 250 DEG C ~ 400 DEG C, normal pressure, liquid phase feed ethanol water mass space velocity (WHSV) 1.2h-1Under the conditions of carry out.
Reaction result is ethanol conversion 98.4% ~ 99.8%, and hydrogen selective is up to 67.5% ~ 71%.
Fig. 1 is the TEM figure that the present embodiment prepares Mock gold sample.There is figure it is found that the Mock gold sample particle diameter synthesized
For 40 ~ 60nm, the high power TEM figure of interpolation in Fig. 1, the direction of lattice fringe is consistent, illustrates that the Mock gold of synthesis is monocrystalline.
Fig. 2 is the XRD spectra that the present embodiment prepares mesoporous silicon oxide clad type Mock gold catalyst.As seen from the figure,
The characteristic diffraction peak and Mock gold of synthesized sample and the diffraction maximum of silica are coincide substantially, do not observe other substances
Diffraction maximum.This illustrates that the mesoporous silicon oxide clad type Mock gold catalyst crystal degree of synthesis well exists without other stray crystals.
Fig. 3 is the small angle XRD spectra of synthetic sample.With the presence of figure it is found that sample apparent (100), (110) crystal face, say
There is bright synthesized mesoporous silicon oxide clad type Mock gold catalyst the good meso-hole structure of the degree of order to exist.
Fig. 4 is the TEM figure that the present embodiment prepares mesoporous silicon oxide clad type Mock gold catalyst.As seen from the figure, institute
The sample of synthesis has apparent core-shell structure, and grain diameter 250nm, shell thickness is about 50 ~ 150nm, shows synthesized
It is complete mesoporous silicon oxide clad type Mock gold catalyst.
Embodiment 2
A kind of preparation method of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, including it is as follows
Step:
1) polyvinylpyrrolidone 0.05g is dissolved in 3mL deionized water, stirs 30min at room temperature, after ultrasonic 10min；Again to
0.04g tryptophan is added in mixed solution, 10min is stirred at room temperature；0.5mL platinum tetrachloride aqueous solution is added into mixed solution again
(30mM) and 1.5mL copper nitrate aqueous solution (30mM), stirs 30min at room temperature；Mixed solution, which is packed into, later has poly- four
In the stainless steel cauldron of vinyl fluoride liner, the static reaction 6h under 200 DEG C of insulating boxs: after reaction, takes out reaction kettle and set
In in quenching slot, 20 DEG C are quickly cooled in 10 DEG C of deionized water；Reaction kettle is opened, polytetrafluoroethylcontainer container is taken out, it will
Crystallization solution in polytetrafluoroethylcontainer container is placed in centrifuge tube, is centrifuged and is washed, and the revolution of centrifuge separation is
10000r/min, disengaging time 15min；Solid sediment is placed in evaporating dish, vacuum oven drying is subsequently placed in, it is dry
Temperature is 50 DEG C.
2) it first disperses 0.01g Mock gold powder in 12mL deionized water, stirs 30min at 25 DEG C；Again by 0.08g
Cetyl trimethylammonium bromide is dissolved in solution, stirs 4h at 25 DEG C；1mL ammonia spirit (25wt%, 0.91g/mL) is added again
Enter in solution, stirs 10min at 25 DEG C；It takes ethyl orthosilicate (0.93g/mL) 1mL to be slowly added dropwise, stirs 2h；After reaction
Gel, which is fitted into centrifuge tube, to be centrifugated and washs, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；By solid
Sediment is placed on filter paper, and in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.It is obtained after drying
Mesoporous silica clad type Mock gold catalyst.
3) 2.395g ammonium nitrate is dissolved in 350mL ethyl alcohol (97wt%) at 60 DEG C, after stirring 30min；In nitrogen atmosphere
Under, it disperses 0.25g mesoporous silica clad type Mock gold catalyst in solution, in 60 DEG C of condensing reflux 4h；It will return
Sample after stream is centrifuged, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；Solid sediment is set
In on filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.Mesoporous dioxy is obtained after drying
SiClx clad type Mock gold catalyst sample 2.
Ethanol steam weight is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Whole reaction evaluating.By the tabletting of mesoporous silicon oxide clad type Mock gold catalyst, it is crushed, is sized to 20 ~ 40 mesh, loadings
0.5g.Reaction is in 250 DEG C ~ 400 DEG C, normal pressure, liquid phase feed ethanol water mass space velocity (WHSV) 1.2h-1Under the conditions of carry out.
Reaction result is ethanol conversion 96.5% ~ 98%, and hydrogen selective is up to 65.3% ~ 67.8%.
Fig. 5 is nitrogen adsorption-desorption figure that the present embodiment prepares mesoporous silicon oxide clad type Mock gold catalyst.By
Figure is it is found that sample there are apparent hysteresis loop, illustrates that there are mesopore orbit structures.
Embodiment 3
A kind of preparation method of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, including it is as follows
Step:
1) polyvinylpyrrolidone 0.04g is dissolved in 3mL deionized water, stirs 30min at room temperature, after ultrasonic 10min；Again to
0.04g glycine is added in mixed solution, 10min is stirred at room temperature；0.8mL six is added into mixed solution again and is hydrated chloroplatinic acid water
Solution (30mM) and 1.2mL copper chloride solution (30mM), stir 30min at room temperature；Mixed solution loading is had later
In the stainless steel cauldron of polytetrafluoroethyllining lining, the static reaction 6h under 200 DEG C of insulating boxs: after reaction, reaction is taken out
Kettle is placed in quenching slot, and 20 DEG C are quickly cooled in 10 DEG C of deionized water；Reaction kettle is opened, polytetrafluoroethylene (PTFE) is taken out and holds
Crystallization solution in polytetrafluoroethylcontainer container is placed in centrifuge tube by device, is centrifuged and is washed, the revolution of centrifuge separation
For 10000r/min, disengaging time 15min；Solid sediment is placed in evaporating dish, vacuum oven drying is subsequently placed in, does
Dry temperature is 50 DEG C.
2) it first disperses 0.01g Mock gold powder in 15mL deionized water, stirs 30min at 25 DEG C；Again by 0.08g
Cetyl trimethylammonium bromide is dissolved in solution, stirs 4h at 25 DEG C；Again by 1.2mL ammonia spirit (25wt%, 0.91g/mL)
It is added in solution, stirs 10min at 25 DEG C；It takes ethyl orthosilicate (0.93g/mL) 1.3mL to be slowly added dropwise, stirs 2h；It will reaction
Gel afterwards, which is fitted into centrifuge tube, to be centrifugated and washs, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；It will
Solid sediment is placed on filter paper, and in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.After drying
Obtain mesoporous silica clad type Mock gold catalyst.
3) 2.386g ammonium nitrate is dissolved in 350mL ethyl alcohol (97wt%) at 60 DEG C, after stirring 30min；In nitrogen atmosphere
Under, it disperses 0.2g mesoporous silica clad type Mock gold catalyst in solution, in 60 DEG C of condensing reflux 4h；It will reflux
Sample afterwards is centrifuged, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；Solid sediment is placed in
On filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.Meso-porous titanium dioxide is obtained after drying
Silicon clad type Mock gold catalyst sample 3.
Ethanol steam weight is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Whole reaction evaluating.By the tabletting of mesoporous silicon oxide clad type Mock gold catalyst, it is crushed, is sized to 20 ~ 40 mesh, loadings
0.5g.Reaction is in 250 DEG C ~ 400 DEG C, normal pressure, liquid phase feed ethanol water mass space velocity (WHSV) 1.2h-1Under the conditions of carry out.
Reaction result is ethanol conversion 97.6% ~ 98.5%, and hydrogen selective is up to 64.5% ~ 65.8%.
Embodiment 4
A kind of preparation method of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, including it is as follows
Step:
1) polyvinylpyrrolidone 0.06g is dissolved in 3mL deionized water, stirs 30min at room temperature, after ultrasonic 10min；Again to
0.04g glycine is added in mixed solution, 10min is stirred at room temperature；1.1mL six is added into mixed solution again and is hydrated chloroplatinic acid water
Solution (30mM) and 0.9mL copper nitrate aqueous solution (30mM), stir 30min at room temperature；Mixed solution loading is had later
In the stainless steel cauldron of polytetrafluoroethyllining lining, the static reaction 6h under 200 DEG C of insulating boxs: after reaction, reaction is taken out
Kettle is placed in quenching slot, and 20 DEG C are quickly cooled in 10 DEG C of deionized water；Reaction kettle is opened, polytetrafluoroethylene (PTFE) is taken out and holds
Crystallization solution in polytetrafluoroethylcontainer container is placed in centrifuge tube by device, is centrifuged and is washed, the revolution of centrifuge separation
For 10000r/min, disengaging time 15min；Solid sediment is placed in evaporating dish, vacuum oven drying is subsequently placed in, does
Dry temperature is 50 DEG C.
2) it first disperses 0.03g Mock gold powder in 15mL deionized water, stirs 30min at 25 DEG C；Again by 0.08g
Cetyl trimethylammonium bromide is dissolved in solution, stirs 4h at 25 DEG C；1mL ammonia spirit (25wt%, 0.91g/mL) is added again
Enter in solution, stirs 10min at 25 DEG C；It takes ethyl orthosilicate (0.93g/mL) 1mL to be slowly added dropwise, stirs 2h；After reaction
Gel, which is fitted into centrifuge tube, to be centrifugated and washs, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；By solid
Sediment is placed on filter paper, and in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.It is obtained after drying
Mesoporous silica clad type Mock gold catalyst.
3) 2.395g ammonium nitrate is dissolved in 350mL ethyl alcohol (97wt%) at 60 DEG C, after stirring 30min；In nitrogen atmosphere
Under, it disperses 0.2g mesoporous silica clad type Mock gold catalyst in solution, in 60 DEG C of condensing reflux 4h；It will reflux
Sample afterwards is centrifuged, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；Solid sediment is placed in
On filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.Meso-porous titanium dioxide is obtained after drying
Silicon clad type Mock gold catalyst sample 4.
Ethanol steam weight is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Whole reaction evaluating.By the tabletting of mesoporous silicon oxide clad type Mock gold catalyst, it is crushed, is sized to 20 ~ 40 mesh, loadings
0.5g.Reaction is in 250 DEG C ~ 400 DEG C, normal pressure, liquid phase feed ethanol water mass space velocity (WHSV) 1.2h-1Under the conditions of carry out.
Reaction result is ethanol conversion 98.8% ~ 99.8%, and hydrogen selective is up to 68.3% ~ 71.2%.
Embodiment 5
A kind of preparation method of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, including it is as follows
Step:
1) polyvinylpyrrolidone 0.015g is dissolved in 1mL deionized water, stirs 30min at room temperature, after ultrasonic 10min；Again
0.05g glycine is added into mixed solution, 10min is stirred at room temperature；0.12mL platinum tetrachloride water is added into mixed solution again
Solution (22.5mM) and 1.88mL copper nitrate aqueous solution (30mM), stir 30min at room temperature；Mixed solution is packed into later and is had
Have in the stainless steel cauldron of polytetrafluoroethyllining lining, the static reaction 6h under 200 DEG C of insulating boxs: after reaction, taking out anti-
It answers kettle to be placed in quenching slot, 20 DEG C is quickly cooled in 10 DEG C of deionized water；Reaction kettle is opened, polytetrafluoroethylene (PTFE) is taken out and holds
Crystallization solution in polytetrafluoroethylcontainer container is placed in centrifuge tube by device, is centrifuged and is washed, the revolution of centrifuge separation
For 10000r/min, disengaging time 15min；Solid sediment is placed in evaporating dish, vacuum oven drying is subsequently placed in, does
Dry temperature is 50 DEG C.
2) it first disperses 0.1g Mock gold powder in 10mL deionized water, stirs 30min at 25 DEG C；Again by 0.03g
Cetyl trimethylammonium bromide is dissolved in solution, stirs 3h at 25 DEG C；Again by 0.55mL ammonia spirit (25wt%, 0.91g/
ML it) is added in solution, stirs 10min at 25 DEG C；It takes ethyl orthosilicate (0.93g/mL) 0.65mL to be slowly added dropwise, stirs 3h；It will
Gel after reaction, which is fitted into centrifuge tube, to be centrifugated and washs, and the revolution of centrifuge separation is 6000r/min, disengaging time
15min；Solid sediment is placed on filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree
10pa.Mesoporous silica clad type Mock gold catalyst is obtained after drying.
3) 1g ammonium nitrate is dissolved in 258mL ethyl alcohol (97wt%) at 60 DEG C, after stirring 30min；In a nitrogen atmosphere, will
0.1g mesoporous silica clad type Mock gold catalyst is scattered in solution, in 60 DEG C of condensing reflux 6h；After reflux
Sample is centrifuged, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；Solid sediment is placed in filter paper
On, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.Mesoporous silicon oxide packet is obtained after drying
Cover formula Mock gold catalyst sample 5.
Ethanol steam weight is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Whole reaction evaluating.By the tabletting of mesoporous silicon oxide clad type Mock gold catalyst, it is crushed, is sized to 20 ~ 40 mesh, loadings
0.5g.Reaction is in 250 DEG C ~ 400 DEG C, normal pressure, liquid phase feed ethanol water mass space velocity (WHSV) 1.2h-1Under the conditions of carry out.
Reaction result is ethanol conversion 94.9% ~ 97.6%, and hydrogen selective is up to 63% ~ 64.9%.
Embodiment 6
A kind of preparation method of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, including it is as follows
Step:
1) polyvinylpyrrolidone 0.015g is dissolved in 8mL deionized water, stirs 30min at room temperature, after ultrasonic 10min；Again
0.05g glycine is added into mixed solution, 10min is stirred at room temperature；It is water-soluble that 0.3mL platinum tetrachloride is added into mixed solution again
Liquid (90mM) and 1.7mL copper nitrate aqueous solution (3mM), stir 30min at room temperature；Mixed solution, which is packed into, later has poly- four
In the stainless steel cauldron of vinyl fluoride liner, the static reaction 3h under 180 DEG C of insulating boxs: after reaction, takes out reaction kettle and set
In in quenching slot, 20 DEG C are quickly cooled in 10 DEG C of deionized water；Reaction kettle is opened, polytetrafluoroethylcontainer container is taken out, it will
Crystallization solution in polytetrafluoroethylcontainer container is placed in centrifuge tube, is centrifuged and is washed, and the revolution of centrifuge separation is
10000r/min, disengaging time 15min；Solid sediment is placed in evaporating dish, vacuum oven drying is subsequently placed in, it is dry
Temperature is 50 DEG C.
2) it first disperses 0.1g Mock gold powder in 10mL deionized water, stirs 30min at 25 DEG C；Again by 0.2g ten
Six alkyl trimethyl ammonium bromides are dissolved in solution, stir 5h at 25 DEG C；Again by 1.65mL ammonia spirit (25wt%, 0.91g/mL)
It is added in solution, stirs 10min at 25 DEG C；It takes ethyl orthosilicate (0.93g/mL) 2.7mL to be slowly added dropwise, stirs 3h；It will reaction
Gel afterwards, which is fitted into centrifuge tube, to be centrifugated and washs, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；It will
Solid sediment is placed on filter paper, and in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.After drying
Obtain mesoporous silica clad type Mock gold catalyst.
3) 3g ammonium nitrate is dissolved in 515mL ethyl alcohol (97wt%) at 60 DEG C, after stirring 30min；In a nitrogen atmosphere, will
0.3g mesoporous silica clad type Mock gold catalyst is scattered in solution, in 60 DEG C of condensing reflux 4h；After reflux
Sample is centrifuged, and the revolution of centrifuge separation is 6000r/min, disengaging time 15min；Solid sediment is placed in filter paper
On, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree 10pa.Mesoporous silicon oxide packet is obtained after drying
Cover formula Mock gold catalyst sample 6.
Ethanol steam weight is carried out to above-mentioned catalyst using atmospheric fixed bed micro-reactor (internal diameter 10mm, length 60cm)
Whole reaction evaluating.By the tabletting of mesoporous silicon oxide clad type Mock gold catalyst, it is crushed, is sized to 20 ~ 40 mesh, loadings
0.5g.Reaction is in 250 DEG C ~ 400 DEG C, normal pressure, liquid phase feed ethanol water mass space velocity (WHSV) 1.2h-1Under the conditions of carry out.
Reaction result is ethanol conversion 95% ~ 97.8%, and hydrogen selective is up to 64.2% ~ 65.7%.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (6)
1. a kind of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, which is characterized in that be by
Nuclear phase Mock gold structure and shell mesoporous silicon oxide structure composition.
2. a kind of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, which is characterized in that described
The content of nuclear phase Mock gold structure is 5 ~ 20wt%, and the content of the shell meso-porous titanium dioxide silicon structure is 80 ~ 95wt%.
3. a kind of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming according to claim 1 or 2
Catalyst, which is characterized in that the crystal particle diameter of the catalyst is 150 ~ 350nm, the thickness of shell meso-porous titanium dioxide silicon structure
For 50 ~ 200nm.
4. a kind of preparation method of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalyst, feature
It is, includes the following steps:
1) nuclear phase Mock gold powder is prepared
2) mesoporous silica clad type Mock gold material is prepared
According to nuclear phase Mock gold powder: deionized water: cetyl trimethylammonium bromide: ammonia spirit: ethyl orthosilicate=
0.01 ~ 0.1:10 ~ 15:0.03 ~ 0.2；The quality proportioning of 0.5 ~ 1.5:0.6 ~ 2.5；First disperse nuclear phase Mock gold powder in
In deionized water, 30min is stirred at 25 DEG C；Cetyl trimethylammonium bromide is dissolved in solution again, 3 ~ 5h is stirred at 25 DEG C；
Ammonia spirit is added in solution again, stirs 10min at 25 DEG C；Finally ethyl orthosilicate is added dropwise in solution, stirs 2h；
Gel after reaction is fitted into centrifuge tube and is centrifugated and washs, the revolution of centrifuge separation is 6000r/min, disengaging time
15min；Solid sediment is placed on filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree
10pa obtains mesoporous silica clad type Mock gold material after dry；
3) mesoporous silicon oxide clad type Mock gold catalyst is prepared
According to mesoporous silica clad type Mock gold material: ethyl alcohol: ammonium nitrate=0.1 ~ 0.3:250 ~ 500:1 ~ 3 quality
Proportion；At 60 DEG C, ammonium nitrate is dissolved in ethyl alcohol, after stirring 30min；In a nitrogen atmosphere, by sample dispersion in solution,
In 60 DEG C of 4 ~ 6h of condensing reflux；Sample after reflux is centrifuged, the revolution of centrifuge separation is 6000r/min, separation
Time 15min；Solid sediment is placed on filter paper, in being dried overnight in vacuum oven, drying temperature is 50 DEG C, vacuum degree
Mesoporous silicon oxide clad type Mock gold catalyst can be obtained after dry in 10pa.
5. a kind of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalysis according to claim 4
The preparation method of agent, which is characterized in that the step 1) prepares the step of nuclear phase Mock gold powder are as follows:
According to deionized water: polyvinylpyrrolidone: amino acids: soluble platinum source: soluble copper source=1 × 103~8
×103: 15 ~ 60:20 ~ 50:0.9 ~ 17.6:0.9 ~ 10 quality proportioning；First polyvinylpyrrolidone is dissolved in deionized water,
30min is stirred at room temperature, after ultrasonic 10min；Amino acids are added into mixed solution again, 10min is stirred at room temperature；Again
Soluble platinum source and soluble copper source are added into mixed solution, stirs 30min at room temperature；Mixed solution loading is had later
In the stainless steel cauldron of polytetrafluoroethyllining lining, the static reaction 3-6h under 180 ~ 200 DEG C of insulating boxs: after reaction, take
Reaction kettle is placed in quenching slot out, and 20 DEG C are quickly cooled in 10 DEG C of deionized water；Reaction kettle is opened, polytetrafluoroethyl-ne is taken out
Reaction product in polytetrafluoroethylcontainer container is placed in centrifuge tube by alkene container, is centrifuged and is washed, centrifuge separation
Revolution is 10000r/min, disengaging time 15min；Solid sediment is placed in evaporating dish, it is dry to be subsequently placed in vacuum oven
Dry, drying temperature is 50 DEG C, vacuum degree 10Pa, drying time 10h, obtains nuclear phase Mock gold powder after dry.
6. a kind of mesoporous silicon oxide clad type Mock gold hydrogen production by ethanol steam reforming catalysis according to claim 5
The preparation method of agent, which is characterized in that soluble platinum source described in step 1) is six hydration chloroplatinic acids or platinum tetrachloride；Step
It is rapid 1) described in soluble copper source be copper nitrate or copper chloride.
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