CN1736604A - Egg shell type metal catalyst, its preparing process and application method - Google Patents
Egg shell type metal catalyst, its preparing process and application method Download PDFInfo
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- CN1736604A CN1736604A CN200510085389.5A CN200510085389A CN1736604A CN 1736604 A CN1736604 A CN 1736604A CN 200510085389 A CN200510085389 A CN 200510085389A CN 1736604 A CN1736604 A CN 1736604A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 74
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 74
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000002360 preparation method Methods 0.000 claims abstract description 47
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 45
- 239000011148 porous material Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 238000001354 calcination Methods 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 40
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 34
- 238000012216 screening Methods 0.000 claims description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- 150000003624 transition metals Chemical class 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000003426 co-catalyst Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000010953 base metal Substances 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 6
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- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 238000009415 formwork Methods 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 101150095510 TMEM35A gene Proteins 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000003863 metallic catalyst Substances 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 239000011796 hollow space material Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000001052 transient effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 59
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 37
- 239000010970 precious metal Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 238000005303 weighing Methods 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 230000009467 reduction Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
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- 239000010949 copper Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- 229910052911 sodium silicate Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000969 carrier Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
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- 238000011068 loading method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
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- 238000001704 evaporation Methods 0.000 description 4
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- 239000011734 sodium Substances 0.000 description 4
- 235000019795 sodium metasilicate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000013528 metallic particle Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 240000007762 Ficus drupacea Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
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- 239000012968 metallocene catalyst Substances 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an egg- shell metallic catalyst and the method for preparation and the application. The catalyst is an egg- shell supported metallic catalyst with a carrier of hollow silica dioxide, which is a hollow material of certain wall and bore diameter, and comprises a noble metal of 0.1%- 5.0% and/ or a transient metal of 5.0%- 40.0%, a non- noble metallic catalyst promoter of 0- 0.5% and a hollow silica dioxide carrier of 60.0%- 99.0%, with the weight ratio of catalyst as a datum level. The egg- shell metallic catalyst can prepare with immersion method or in- situ supporting method. The catalyst has good metal dispersibility, and the metal particle diameter is minor, dispersing on the external surface, inner surface and in the pore passage. And the egg- shell metallic catalyst can catalyze CO and CO2 to prepare lower carbon number hydrocarbons and alcohol, and it also can catalyze olefin and alkyne selectively.
Description
Technical field
The present invention relates to a kind of egg shell type metal catalyst, particularly a kind of is the egg shell type metal catalyst and preparation method thereof and the application in catalytic hydrogenation reaction of carrier with silica.
Background technology
Be extensive use of loaded noble metal catalyst in the selective catalytic hydrogenation reaction in the petrochemical industry, prepare monoolefine etc. as selective catalytic hydrogenations such as alkadienes or alkynes.This class reaction has the advantages that reaction speed is fast, side reaction is many, and the purpose product is intermediate product often, and degree of depth hydrogenation is not expected.Theory and practice proves absolutely, to this big class catalytic reaction process, under the constant situation of total amount, the noble metal active component is compared with the equally distributed catalyst of active component at the catalyst of intragranular non-uniform Distribution (as eggshell type, yolk type), can significantly improve apparent activity, selectivity and the anti-middle toxicity of catalyst granules.When spreading in catalyst exists, the catalyst that eggshell type distributes has the highest catalytic activity; System with parallel side reaction, when the progression of main reaction during greater than the progression of side reaction, active component is distributed near the particle outer surface, can improve the selectivity of main reaction etc.Yet, industrial (solid) catalyst commonly used, its active component is the inner surface that is evenly distributed in porous carrier mostly.Obviously, the equally distributed catalyst of this active component, not only reaction effect is bad, and has wasted the noble metal resource in a large number.Therefore, the egg-shell catalyst with suitable active distribution becomes the ideal selection of this class reaction, develops this special-shaped catalyst and has great application prospect.
CO and CO
2Catalytic hydrogenation reaction can be converted into inorganic raw material and be widely used and higher lower carbon number hydrocarbons of actual application value or alcohol etc., not only made full use of CO abundant in the natural environment
2And coal resources, also can reduce the CO in the environment
2Thereby, the influence that alleviates greenhouse effects.There is the abundant in coal resource in China, can be synthesis gas (CO+H with coal conversion by Water gas shift/WGS
2), thereby change higher and wider hydro carbons or the alcohols of prospect of using value into by the catalytic action of catalyst.For catalytic hydrogenation, the effect of noble metal catalyst is exactly to H by noble metal granule
2, CO suction-operated, and react thereon, and can improve activity of such catalysts and selectivity by adding suitable co-catalyst.Because the costing an arm and a leg of platinum (Pt), palladium (Pd), rhodium noble metals such as (Rh), scarcity of resources, usually should take suitable preparation method and process conditions to reduce the particle size of noble metal, increase the decentralization of noble metal on carrier, improve activity of such catalysts and utilization rate.In addition, the transition metal of VIII family is a kind of effective catalyst as copper (Cu), zinc (Zn), nickel (Ni), active higher in catalytic hydrogenation reaction particularly, and the Raney nickel of preparation support type can make catalytic active center disperse, and improves catalytic activity.Carrier that can metal supported catalyst is generally selected SiO
2, γ-Al
2O
3, molecular sieve, zeolite etc., co-catalyst is generally selected the base metal of alkali metal, alkaline-earth metal or VIB and VIIIB family.
In the last few years, domestic and international many researchers had attempted several different methods and preparing carriers load type metal catalyst.Tanaka etc. (Tanaka S.Applied Catalysis A:General, 2002,229:165-174.) on silica gel, deposit supported precious metal palladium with sol-gel process.Adopt this method, Pd can be dispersed in the silica gel well, and granularity is less, the Pd/SiO of this kind method preparation
2The more traditional catalyst prepared metallic particles of catalyst is difficult for reuniting, so even still be dispersity through long-time high-temperature process.But, the catalyst that adopts this kind method to prepare, the metal active center is evenly distributed on the catalyst carrier, can not play control action to fast reaction.
Venezia etc. (Venezia A M.Jouranl of Catalysis, 1999,182:449-455.) having introduced with the float stone is preparing carriers binary precious metals ag-Pd catalyst, and the composite catalyst of transition metal Cu and precious metals pd.Adopt the binary composite catalyst of immersion process for preparing, because the sequencing difference of load, catalyst characterization just embodies different results.This catalyst is to be carrier with the float stone, and the catalyst carrier that adopts with the present invention is different, but it still can not obtain the catalyst that active component is the eggshell type distribution.
Chang etc. (Chang June-Cheng, Chou Tse-Chuan.Applied Catalysis A:General, 1997,156:193-205.) prepared the Pd/Al that a kind of eggshell type distributes
2O
3Catalyst, and be applied to the selective hydrogenation of isoprene.Gangwal etc. (Gangwal V R, van der Schaaf J, Kuster BF M, Schouten J C.Catalysis Today, 2004,96:223-234.) prepared Pt/ activated-carbon catalyst that eggshell type distributes and the oxidation that is applied to ethanol.Though their catalytic activity is all higher, its preparation needs that all loading condition is carried out certain control could obtain the noble metal catalyst that active component is the eggshell type distribution.And these catalyst generally all are used for gas-liquid reaction, seldom are used for gas-solid/liquid/gas reactions.This activity of such catalysts component mainly is distributed in the extexine of carrier, is eggshell type and distributes, and is still solid carrier active carbon in the inside of catalyst.On structure, there is basic difference in the egg-shell catalyst of this kind egg-shell catalyst and the present invention's preparation, because the egg-shell catalyst of the present invention's preparation is with hollow SiO
2Be carrier, active component is distributed in outer surface, inner surface and the duct of hollow carrier, and catalyst inside is cavity.
Domestic have lot of documents (Naruhito, room, etc. petrochemical industry, 2003,32 (1): 5-8; Hong Chuanqing, etc. chemistry of fuel journal, 2001,29 (4): 355-359; Wang Zhaoqian, etc. the gas chemical industry, 2003,29:16-19.) reported that traditional methyl alcohol synthesizes the preparation and the catalytic performance of copper-zinc catalyst.These catalyst mainly are with Al
2O
3Be carrier, by the catalytic action of interaction between active component and the carrier and active component, it is smooth to make that catalytic hydrogenation prepares methyl alcohol.But adopt this kind catalyst, its reaction condition is had relatively high expectations, reaction pressure generally need be controlled at 5～20MPa, the needed reaction pressure of the catalyst that has is higher, particularly in the industrial production methanol process, maximum pressure will reach 150MPa, and this just has higher requirement to reactor, and energy consumption also increases substantially simultaneously.Copper-based catalysts is a kind of low pressure catalyst, and its key component is CuO/ZnO/Al
2O
3, successively to succeed in developing by Britain ICI company and German Lurgi company, operating temperature is 500～530K, pressure but has only 5～10MPa, and is more much lower than traditional synthesis technique temperature, favourable to the methyl alcohol molecular balance.
The decentralization that has just improved catalyst active center that the method for preparing catalyst of mentioning in the above document has, but the metal active central distribution is more even as a complete unit, still have a large amount of activated centres can not play catalytic action in catalyst granules inside, thereby cause the waste of metal active constituent.Though and the preparation method who has can control the eggshell type distribution of active component, but its loading condition is generally all comparatively strict, reaction condition is had relatively high expectations, particularly in the reaction of CO hydrogenation preparing methyl alcohol, adopt copper-zinc catalyst, the entire reaction condition need increase substantially, and wherein reaction pressure is had relatively high expectations, its required minimum pressure also needs 5MPa, and the conversion ratio of CO is relatively low simultaneously.
The prepared metallic catalyst of the present invention is the catalyst of a kind of metal active center non-uniform Distribution, and it is to have the SiO of hollow-core construction
2Be carrier, a certain amount of metal of load is prepared from its wall.Therefore, be easy to realize that the eggshell type of active component distributes, and can significantly reduce the consumption of metal, and can give full play to the catalytic activity of metal active constituent, can also be applied to targetedly simultaneously some solution-airs gentle-the fast reaction system of gas.In the technology of CO hydrogenation preparing methyl alcohol, adopt with hollow SiO
2Be the catalyst of preparing carriers, reaction pressure can be controlled at 1.5～5.0MPa, and reaction temperature is 200～300 ℃.Compare with traditional copper-zinc catalyst, reaction condition obviously reduces, and the conversion ratio of the selectivity of methyl alcohol and CO all increases, and illustrates that this kind catalyst is applicable to synthesizing methanol under low temperature, the low pressure.
SiO about hollow-core construction
2Carrier has a detailed description in the patent of the previous application of the applicant (Beijing University of Chemical Technology).In Chinese invention patent Shen Qing Publication specification CN 1445311A, introduced nanometer CaCO
3/ SiO
2The preparation method of composite.With the nano-calcium carbonate is template, is the silicon source with the sodium metasilicate, and the surface that is reflected at calcium carbonate by watery hydrochloric acid and sodium metasilicate not only can coat one deck SiO
2, granular size, wall thickness and the grain shape that can also regulate and control hollow silicon dioxide according to the granular size and the grain shape of calcium carbonate.In Chinese invention patent Shen Qing Publication specification CN 1511785A, introduced with the nano-calcium carbonate is template, the method for preparing the hollow silicon dioxide mesoporous material with the sodium metasilicate for the silicon source, the hollow silicon dioxide mesoporous material particle diameter of its preparation is 50～120nm, wall thickness is 10～15nm, and average pore size is 2～5nm.In Chinese invention patent application 200410098068.4, introduced by the individual particle hollow silicon dioxide and prepared the hollow silicon dioxide granule, and hollow silicon dioxide granule load metallocene catalyst, and the application in olefinic polyreaction.And with hollow SiO
2Be the egg-shell catalyst of carrier to load metal active component, and be used for CO hydrogenation preparing methyl alcohol, yet there are no report.
Summary of the invention
The objective of the invention is with coated with silica to as on the nano-calcium carbonate of template with the spherical hollow or tubular, hollow SiO of final preparation
2, and with this hollow SiO
2Egg shell type metal catalyst for carrier.Another object of the present invention provides the preparation method of this egg shell type metal catalyst.This catalyst has the good metal dispersiveness, and metallic particles is less, and metallic particles can be dispersed in hollow SiO
2Outer surface, inner surface and duct in, be applicable to that hydrogenation reaction prepares the reaction of methyl alcohol.
The present invention relates to a kind of carrier of egg shell type metal catalyst---hollow SiO
2, it has hollow-core construction, is shaped as spherical or tubulose.
The present invention relates to above-mentioned hollow silicon dioxide is carrier, adopts infusion process or original position load legal system to be equipped with egg shell type metal and structural characterization thereof.
The catalyst that the invention still further relates to the above-mentioned preparation of employing is applied to the reaction of CO hydrogenation preparing methyl alcohol.
The technical scheme of catalyst of the present invention is:
A kind of egg shell type metal catalyst is made up of silica supports, noble metal and/or transition metal, selectable base metal co-catalyst, and wherein said carrier is the silica of hollow-core construction.With catalyst weight percentage is benchmark, and it consists of 0.1%～5.0% noble metal and/or 5.0%～40.0% transition metal, 0～0.5% base metal co-catalyst, 60.0%～99.0% hollow silicon dioxide carrier.Wherein said noble metal is selected from one or more among Pd, Pt, the Rh, described transition metal is selected from one or more among Ni, Cu, the Zn, and described base metal co-catalyst is selected from one or more in alkali metal, alkaline-earth metal, group vib element and other transition metal.
Hollow SiO among the present invention
2The preparation method of carrier has detailed introduction in Chinese invention patent Shen Qing Publication specification CN1445311A and CN 1511785A, be template with the nano-calcium carbonate promptly, prepares the hollow silicon dioxide mesoporous material with the sodium metasilicate for the silicon source.The application adopts spherical particle or the tubular particle SiO with hollow-core construction
2Carrier has bigger pore volume and specific area, and has the duct of queueing discipline.Wherein spherical hollow SiO
2Specific area be 500～1500m
2/ g is preferably 500～1000m
2/ g; Pore volume is 0.3～1.0mL/g, is preferably 0.5～0.9mL/g.And tubular, hollow SiO
2The specific area of particle is 400～1000m
2/ g is preferably 500～800m
2/ g; Pore volume is 0.3～1.0mL/g, is preferably 0.5～0.8mL/g; Diameter is 80～150nm, and length is 1～3 μ m.
The technical scheme of Preparation of catalysts method of the present invention is:
A kind of preparation method of egg shell type metal catalyst, in turn include the following steps: the hollow silicon dioxide carrier is joined in acetate, nitrate, sulfate or the halid solution of at least a noble metal and/or at least a transition metal, and fully mix with it, temperature is controlled at 20～80 ℃; Load is filtered after finishing, and is warmed up to 80～130 ℃ with 10～20 ℃/min, dry 3～15h; With dried powder screening, be warmed up to 400～500 ℃ with 1～5 ℃/min at last, calcining 3～12h.
A kind of preparation method of egg shell type metal catalyst, in turn include the following steps: adopt polymethyl methacrylate to make organic formwork, ethyl orthosilicate is the silicon source, the acetate of at least a noble metal and/or at least a transition metal, nitrate, sulfate or halide are presoma, with the corresponding acid of halide or salt be hydrolytic reagent and precipitating reagent, control pH value is between 1～3, and hydrolysis 10～20h is to the solution clear; Filter, be warmed up to 95～115 ℃ with 10～20 ℃/min then, dry 5～10h; With dried powder screening, be warmed up to 400～600 ℃ with 1～5 ℃/min at last, calcining 3～7h.
A kind of preparation method of egg shell type metal catalyst in turn includes the following steps: acetate, nitrate, sulfate or the halid solution of transition metal are joined hollow SiO
2In the colloidal solution of carrier, and fully stir with it, drip simultaneously and be selected from Na
2CO
3, NaHCO
3Perhaps NH
3HCO
3Precipitating reagent, mixing speed is controlled at 400～600r/min, the pH value of maintenance system is between 8～10, mixing time is 12～24h; Load is filtered after finishing, and is warmed up to 90～110 ℃ with 10～20 ℃/min then, dry 3～12h; Dried powder sieves with standard screen, and the powder after the screening is carried out calcination processing, and calcining heat is 450～500 ℃, and heating rate is 1～5 ℃/min, and calcination time is 3～10h.
A kind of preparation method of egg shell type metal catalyst, in turn include the following steps: will be according to above-mentioned 3 kinds of catalyst that method makes, further join in the solution of non-noble metal halide, nitrate or carbonate, and fully mix with it, temperature is controlled at 20～80 ℃; Load is filtered after finishing, and is warmed up to 90～110 ℃ with 10～20 ℃/min, dry 3～12h; With dried powder screening, be warmed up to 400～450 ℃ with 1～5 ℃/min at last, calcining 3～10h.
The present invention gives the process conditions that aforementioned catalyst is applied to CO hydrogenation preparing methyl alcohol, and promptly reaction temperature is 200～300 ℃, reaction pressure 1.5～5.0MPa, H
2With the volume ratio of CO be (1.5～3.0): 1.
Below preparation method of the present invention is described in detail:
A certain amount of precious metal salt or halide are mixed with the aqueous solution, and for noble metal halide, general corresponding acid and the deionized water of adopting dissolves, and course of dissolution needs heating, boiling, until solution clarification, transparent.Take by weighing a certain amount of hollow silicon dioxide carrier, join in the above-mentioned precious metal solution, can stir simultaneously, mixing time generally is controlled at 2～15h, preferred 5～10h; The temperature of while control load system, temperature is controlled at 20～80 ℃, preferred 30～50 ℃.After the load of load system finishes, filter, dry, screening and calcination processing, can obtain the egg-shell catalyst of carried noble metal.The dry treatment temperature of this method is 80～130 ℃, and be 3～15h drying time, and heating rate is 10～20 ℃/min.Dried powder sieves with standard screen, and the powder after the screening is carried out calcination processing, and calcining heat is 400～500 ℃, and heating rate is 1～5 ℃/min, and calcination time is 3～12h.
The present invention also provides the another kind of preparation method of eggshell type noble metal catalyst.Promptly adopt a certain amount of polymethyl methacrylate to make organic formwork, proportionally adding a certain amount of ethyl orthosilicate is the silicon source, with precious metal salt or halide presoma as noble metal catalyst, with the corresponding acid of precious metal salt or halide be hydrolytic reagent and precipitating reagent, at room temperature stir hydrolysis, load, after filtration, dry, screening and calcination processing, can obtain the eggshell type noble metal catalyst.The mass fraction of the polymethyl methacrylate emulsion of this method is 25%～45%, the mass fraction of Si is 28% in the ethyl orthosilicate, in precious metal chloride, add deionized water and corresponding acid, the pH value of reaction system generally is controlled between 1～3, heating, boiling, hydrolysis 10～20h until solution clarification, transparent, and treats that it reduces to room temperature; Filter, drying, baking temperature is 95～115 ℃, and heating rate is 10～20 ℃/min, and be 5～10h drying time; With dried powder screening back calcining, calcining heat is 400～600 ℃, and heating rate is 1～5 ℃/min, and calcination time is 3～7h, can obtain the eggshell type noble metal catalyst.
The present invention also provides a kind of preparation method of eggshell type noble metal catalyst.Take by weighing a certain amount of precious metal salt or halide and be mixed with the aqueous solution, obtain required precious metal salt solution.Take by weighing a certain amount of spherical hollow SiO
2Carrier slowly splashes into this solution in the spherical hollow silicon dioxide support powder then, just forms pasty state and does not have excess liquid to occur.Place 0.5～3.0h under the room temperature and be placed on 80～110 ℃ of down dry 8～12h, wait moisture evaporation intact after with the dry powder that obtains at 450～550 ℃ of calcining 2～4h down, its heating rate is 2～8 ℃/min, can obtain the eggshell type noble metal catalyst.
Eggshell type noble metal catalyst with above-mentioned preparation is a carrier, and further the load non-noble metal components is as co-catalyst, thereby makes the eggshell type noble metal catalyst that base metal helps catalysis.Halide, nitrate or dissolves carbonate with a certain amount of base metal (as alkali metal, alkaline-earth metal or transition metal) are made into certain density solution.Get a certain amount of above-mentioned base metal salting liquid, take by weighing a certain amount of above-mentioned eggshell type noble metal catalyst again, carry out non-noble metal load.Can stir during load, mixing time is 2～15h, and load temperature is 20～80 ℃, preferred 30～50 ℃.After load finishes, filter, dry, screening and calcination processing, can obtain the eggshell type noble metal catalyst that load has the base metal co-catalyst.The dry treatment temperature of this method is 90～110 ℃, and be 3～12h drying time, and heating rate is 10～20 ℃/min.Dried powder sieves with standard screen, powder after the screening is carried out calcination processing, and calcining heat is 400～450 ℃, and heating rate is 1～5 ℃/min, calcination time is 3～10h, and can obtain base metal is the eggshell type noble metal catalyst of co-catalyst.
The present invention also provides a kind of preparation method of eggshell type transition-metal catalyst.Acetate, nitrate, sulfate or chloride deionized water dissolving with a certain amount of transition metal add a certain amount of hollow SiO again
2Carrier stirs dip loading, drips simultaneously and is selected from Na
2CO
3, NaHCO
3Perhaps NH
3HCO
3Precipitating reagent, mixing speed is controlled at 400～600r/min, the pH value of maintenance system is between 8～10, mixing time is 12～24h.After the load, filter, dry, screening and calcination processing, can obtain the egg-shell catalyst of nickel-loaded.The dry treatment temperature of this method is 90～110 ℃, and be 3～12h drying time, and heating rate is 10～20 ℃/min.Dried powder sieves with standard screen, and the powder after the screening is carried out calcination processing, and calcining heat is 400～450 ℃, and heating rate is 1～5 ℃/min, and calcination time is 3～10h.
The invention provides a kind of preparation method of eggshell type bimetallic catalyst, is that example is described below with the copper-zinc catalyst.Nitrate, chloride, sulfate or acetate deionized water dissolving with a certain amount of copper and zinc are mixed with mixed solution, with a certain amount of hollow SiO
2Carrier is mixed with colloid with proper amount of deionized water, and the mixed solution of mantoquita and zinc salt is joined SiO
2In the colloid, stir, mixing speed is 400～600r/min, drips certain density Na simultaneously
2CO
3Solution, the pH value of maintenance system are between 8～10, and mixing time is 5～12h.After the load, filter, dry, screening and calcination processing, can obtain the egg-shell catalyst of loaded Cu-Zn.The dry treatment temperature of this method is 90～110 ℃, and be 3～12h drying time, and heating rate is 10～20 ℃/min.Dried powder sieves with standard screen, and the powder after the screening is carried out calcination processing, and calcining heat is 450～500 ℃, and heating rate is 1～5 ℃/min, and calcination time is 3～10h.
Catalyst of the present invention is used for the process conditions that the CO hydrogenation reaction prepares methyl alcohol: 200～300 ℃ of reaction temperatures, reaction pressure 1.5～5.0MPa, H
2With the volume ratio of CO be (1.5～3.0): 1.The method that reactivity is tested is: at first a certain amount of catalyst is filled in the micro fixed-bed reactor, adopt High Purity Hydrogen to reduce, reduction temperature is 380～420 ℃, and the reduction heating rate is 2～8 ℃/min, hydrogen flowing quantity is 20～40mL/min, and the recovery time is 2～5h.Reduction cools the temperature to reaction temperature after finishing, and feeds reacting gas CO and H simultaneously
2, H
2With the volume ratio of CO be (1.5～3.0): 1, simultaneously reaction pressure is transferred to 1.5～5.0MPa, product is analyzed by gas-chromatography is online.
Egg shell type metal catalyst provided by the invention is particularly suitable for the reaction that the CO catalytic hydrogenation prepares methyl alcohol.With traditional silica gel is that the catalyst of preparing carriers is compared, and its reaction pressure significantly reduces, and the reaction pressure of this kind catalyst only needs 1.5～5.0MPa, and the required pressure minimum of traditional catalyst is also wanted 5MPa.Simultaneously, the conversion ratio of CO significantly improves, and the one way maximum conversion of CO can reach 68%, and the selectivity of methyl alcohol is 100%; And the one way maximum conversion of general catalyst is about 40%, and the selectivity of methyl alcohol is about 95%.Therefore, adopt hollow SiO
2Make the catalytic hydrogenation catalyst of carrier, not only can reduce reaction condition, can also improve the selectivity of conversion ratio and the methyl alcohol of CO.
Description of drawings
Fig. 1 is the TEM photo of spherical hollow silicon dioxide.
Fig. 2 is the TEM photo of tubular, hollow silica.
Fig. 3 is that spherical hollow silicon dioxide is the TEM photo of the eggshell type precious metals palladium catalyst of carrier.
Fig. 4 is that spherical hollow silicon dioxide is the TEM photo of the eggshell type precious metals platinum catalyst of carrier.
Fig. 5 is that tubular, hollow silica is the TEM photo of the eggshell type precious metals platinum catalyst of carrier.
Fig. 6 is that spherical hollow silicon dioxide is the TEM photo of the eggshell type transition metal Raney nickel of carrier.
Fig. 7 is a reaction temperature optionally to be influenced eggshell type Raney nickel CO conversion ratio and product methyl alcohol in the CO hydrogenation reaction.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
Adopt the cube nano-calcium carbonate of high-gravity technology preparation to be mixed with the suspension that concentration is 0.8mol/L hypergravity ERC of the Ministry of Education of Beijing University of Chemical Technology, get 1000mL nano-calcium carbonate suspension and place reactor, and beginning heat temperature raising and stirring, mixing speed is controlled at 400～500r/min; Compound concentration is the sodium silicate solution 500mL of 0.68mol/L and the dilute hydrochloric acid solution of 10wt%.When temperature is raised to 80 ℃, begin to add sodium silicate solution, add watery hydrochloric acid simultaneously, the pH of regulation system generates CaCO between 8.5～9.5
3/ SiO
2The nucleocapsid structure material.After treating that sodium silicate solution all is added drop-wise in the system, stop to add acid, and stir ageing under this reaction temperature, digestion time is controlled at 4h, so that make SiO
2At CaCO
3Surface deposition, curing.Slurry after the ageing is through filtering, washing, and dry 12h under 105 ℃ pulverizes the back with the screening of 250 mesh standard sieves, calcines 4 ℃/min of programming rate, 600～700 ℃ of calcining heats, calcination time 6h then in Muffle furnace.Through the powder after the calcining,, remove CaCO with the watery hydrochloric acid 500mL dissolving of 20wt%
3Template, and dissolve 5h under less than 1 situation in the pH value; Through washing, filtration, dry under 105 ℃, screening promptly obtains spherical hollow silicon dioxide particle at last.The specific area of spherical hollow silicon dioxide particle is 500～1500m
2/ g, pore volume are 0.3～1.0mL/g.Fig. 1 is the TEM photo of this spherical hollow silicon dioxide.
Embodiment 2
Adopt the acicular nanometer calcium carbonate of high-gravity technology preparation to be mixed with the suspension that concentration is 0.8mol/L hypergravity ERC of the Ministry of Education of Beijing University of Chemical Technology, get 1000mL nano-calcium carbonate suspension and place reactor, stir, mixing speed is controlled at 400～500r/min; According to SiO
2/ CaCO
3Mass ratio is 0.2 the ratio ethyl orthosilicate (containing the Si mass fraction is 28%) that takes by weighing 26.7g with the ethanol dissolving, and the ethanolic solution of ethyl orthosilicate is joined in the calcium carbonate slurry, adds the concentrated ammonia liquor of the 17wt% of 100mL again, at room temperature stirs 12h.Reacted slurry is through filtering, washing, and dry 12h under 105 ℃ pulverizes the back with the screening of 250 mesh standard sieves, calcines 4 ℃/min of programming rate, 600～700 ℃ of calcining heats, calcination time 6h then in Muffle furnace.Through the powder after the calcining,, remove CaCO with the watery hydrochloric acid 500mL dissolving of 20wt%
3Template, and dissolve 5h under less than 1 situation in the pH value; Through washing, filtration, dry under 105 ℃, screening promptly obtains the tubular, hollow silica dioxide granule at last.Tubular, hollow SiO
2The specific area of particle is 400～1000m
2/ g, pore volume are 0.3～1.0mL/g, and diameter is 80～150nm, and length is 1～3 μ m.Fig. 2 is the TEM photo of this tubular, hollow silica.
Embodiment 3
Take by weighing 0.1666g PdCl
2Pressed powder adds the concentrated hydrochloric acid of 10mL deionized water and 10mL 35%, carries out heating for dissolving after shaking up, and is heated to boiling, until solution becomes must clarify, transparent.With PdCl
2Solution is cooled to room temperature, takes by weighing the spherical hollow SiO of 2g by embodiment 1 preparation
2Carrier joins PdCl
2In the solution, begin simultaneously to stir, flood.Mixing time is 12h, and the control load temperature is about 35 ℃, carries out vacuum filtration then, and through washing to remove the Pd in the not load
2+, the filter cake after the filtration is dry under 120 ℃, and heating rate is 10 ℃/min, and be 12h drying time.Dried powder sieves with 250 mesh standard sieves, and the powder after the screening is calcined, and calcining heat is 450 ℃, and heating rate is 1 ℃/min, and calcination time is 6h, can obtain Pd load quality mark and be 3.35% eggshell type precious metals palladium catalyst.Fig. 3 is the TEM photo of this catalyst.
Embodiment 4
Take by weighing the Ca (NO of 0.149g
3)
24H
2O, place the interior small quantity of deionized water that adds of beaker of 50mL to dissolve, all transfer in the volumetric flask of 100mL, repeatedly wash beaker with small quantity of deionized water, solution after each washing is all transferred in the volumetric flask, drip deionized water until scale to volumetric flask at last, shake up then, just can obtain concentration is the Ca (NO of 0.00631mol/L
3)
2Solution.Taking by weighing 0.4g is 3.35% eggshell type precious metals pd catalyst by embodiment 3 prepared Pd mass fractions, is placed in the beaker of 50mL, pipettes the Ca (NO of 10mL 0.00631mol/L with the 10mL pipette
3)
2Solution adds small quantity of deionized water again, makes catalyst fully flood, and stirs simultaneously, and mixing time is 5h.Last heating evaporation all evaporates the moisture in the system, and at 105 ℃ of following dry 10h, heating rate is 10 ℃/min then, and dried filter cake sieves with 250 mesh standard sieves, and the powder after the screening is in 450 ℃ of calcining 6h, and heating rate is 1 ℃/min.Can obtain with the alkaline earth metals calcium after calcining finishes is that co-catalyst, calcareous amount mark are 0.5% eggshell type precious metals palladium catalyst.
Embodiment 5
Take by weighing the Li of 0.125g
2CO
3Place the interior small quantity of deionized water that adds of beaker of 50mL to dissolve, all transfer in the volumetric flask of 100mL, repeatedly wash beaker with small quantity of deionized water, solution after each washing is all transferred in the volumetric flask, drip deionized water until scale to volumetric flask at last, shake up then, just can obtain the Li that concentration is 0.02557mol/L
2CO
3Solution.Taking by weighing 0.5g is 3.35% eggshell type precious metals pd catalyst by embodiment 3 prepared Pd mass fractions, is placed in the beaker of 50mL, pipettes the above-mentioned Li of 6mL with pipette
2CO
3Solution adds small quantity of deionized water again, makes catalyst fully flood, and stirs simultaneously, and mixing time is 5h.Last heating evaporation all evaporates the moisture in the system, and at 105 ℃ of following dry 10h, heating rate is 10 ℃/min then, and dried filter cake sieves with 250 mesh standard sieves, and the powder after the screening is in 450 ℃ of calcining 6h, and heating rate is 1 ℃/min.Can obtain with the alkali metal lithium after calcining finishes is that the mass fraction of co-catalyst, lithium is 0.5% eggshell type precious metals palladium catalyst.
Embodiment 6
Take by weighing 0.1343g PdCl
2Pressed powder adds 10mL deionized water and 10mL concentrated hydrochloric acid, and heating for dissolving is heated to boiling, until solution clarification, transparent; Take by weighing the 25g mass fraction and be 40% polymethyl methacrylate, it is transferred in the volumetric flask of 500mL, add the 200mL deionized water, the Si mass fraction that adds 16.4g again is 28% ethyl orthosilicate, at last with PdCl
2Being added in the above-mentioned system of solution drips an amount of watery hydrochloric acid simultaneously, and the pH value of reaction system is maintained about 1, at room temperature stirs hydrolysis, and hydrolysis time is 12h.Because hydrochloric acid in the system and ethyl orthosilicate reaction generate SiO
2, so hydrochloric acid plays the effect of hydrolytic reagent and precipitating reagent, and the SiO that generates
2And Pd
2+Fully mix, be deposited on the surface of polymethyl methacrylate, product nucleus shell structure, precious metals pd just load to spherical SiO
2On the carrier.After reaction finished, after filtration, filter cake is dry 10h under 105 ℃, heating rate is 10 ℃/min, after dried filter cake sieves through 250 mesh standard sieves, in 450 ℃ of calcinings, calcination time is 6h, and heating rate is 1 ℃/min, can obtain the eggshell type noble metal catalyst of supported precious metal palladium.
Embodiment 7
Take by weighing the H of 0.0560g
2PtCl
66H
2The O solid is dissolved in the 10mL deionized water, adds the concentrated hydrochloric acid of 1mL35% then.0.5g is added in the above-mentioned solution by the spherical hollow silicon dioxide carrier of embodiment 1 preparation, filters after leaving standstill dipping 12h, the platinum ion of not load is removed in washing, filter cake in 80 ℃ dry down, heating rate is 10 ℃/min.Calcine 3h at last under 500 ℃, its heating rate is 1 ℃/min, can obtain the eggshell type noble metal catalyst of load platinum.Fig. 4 is the TEM photo of this catalyst.
Embodiment 8
Take by weighing the H of 0.1120g
2PtCl
66H
2The O solid is dissolved in the 19.8mL deionized water, drips the ammonia spirit of 0.2mL then, and this moment, the pH value of solution was about 10; 0.4g is added in the above-mentioned solution by the tubular, hollow silica supports of embodiment 2 preparation subsequently again, filters after leaving standstill dipping 12h, the washing back is dry down in 80 ℃.Calcine at last, earlier, under this temperature, keep 3h again, promptly obtain the tubulose egg-shell catalyst of load platinum with the speed temperature programming to 500 of 2 ℃/min ℃.
Embodiment 9
Take by weighing the H of 0.0446g
2PtCl
66H
2The O solid is dissolved in the 8mL deionized water, obtains required platinum acid chloride solution.Then this solution is slowly splashed in the spherical hollow silicon dioxide support powder of 1.1g by embodiment 1 preparation, just form pasty state and do not have excess liquid to occur.Place 1h under the room temperature and be placed on 90 ℃ of dry 10h down, wait moisture evaporation intact after with the dry powder that obtains at 500 ℃ of calcining 3h down, its heating rate is 2 ℃/min, promptly obtains the eggshell type noble metal catalyst of load platinum.
Embodiment 10
Take by weighing 0.99g Ni (NO
3)
26H
2The O solid with the proper amount of deionized water dissolving, obtains nickel nitrate solution.With the spherical hollow SiO of 2g by embodiment 1 preparation
2Carrier joins in the above-mentioned solution, stirs dip loading 12h, after the filtration, dry under 105 ℃, its heating rate is 10 ℃/min, at last dried powder is carried out high-temperature roasting, sintering temperature is 400 ℃, and its heating rate is 1 ℃/min, obtains at last with spherical hollow SiO
2Egg-shell catalyst for the nickel-loaded of carrier.Fig. 5 is the TEM photo of this catalyst.
Embodiment 11
Take by weighing 0.1017g PdCl
2Pressed powder adds the concentrated hydrochloric acid of 10mL deionized water and 10mL 35%, carries out heating for dissolving after shaking up, and is heated to boiling, until solution becomes must clarify, transparent.Ni (the NO that adds 0.4955g again
3)
26H
2O joins PdCl
2In the solution, stir, treat that it dissolves fully, after temperature reduces to room temperature, add the spherical hollow SiO of 2 g by embodiment 1 preparation
2Carrier stirs dip loading 12h, and is after the filtration, dry down in 105 ℃, its heating rate is 10 ℃/min, at last dried powder is carried out high-temperature roasting, and sintering temperature is 450 ℃, its heating rate is 1 ℃/min, and calcination time is 4h, obtains at last with spherical hollow SiO
2Egg-shell catalyst for the nickel-loaded-palladium of carrier.
Embodiment 12
Take by weighing the Cu (NO of 11.74g
3)
2Zn (NO with 11.63g
3)
2, add deionized water and be mixed with mixed solution.Take by weighing the spherical hollow SiO of 2g again by embodiment 1 preparation
2Carrier, the sub-water of degranulation that adds 20mL is mixed with colloid, and it is transferred in the flask of 500mL, stirs, and mixing speed is 500r/min.At room temperature the mixed solution with copper nitrate and zinc nitrate joins SiO
2In the colloid, drip certain density Na simultaneously
2CO
3Solution, the pH value of maintenance system are between 9～10, and the reaction time is 10h.After question response finishes, overanxious, and with the ethanol washing, in 95 ℃ of dry 8h down, screening, 500 ℃ of calcinings down, calcination time is 4h, can obtain spherical hollow SiO
2The egg-shell catalyst of load copper-zinc.
Embodiment 13
Take by weighing the eggshell type noble metal catalyst of 0.5g by the load P dO of embodiment 3 preparations, it is filled in volume is that 5mL, internal diameter are in the micro fixed-bed reactor of 10mm, adopting purity is that 99.999% High Purity Hydrogen is carried out hydrogen reducing, adopt temperature programming during reduction, heating rate is 2 ℃/min, and reduction temperature is 400 ℃, and hydrogen flowing quantity is 30mL/min, recovery time is 3h, can obtain through pretreated eggshell type precious metals palladium catalyst.Reduction cools the temperature to 220 ℃ after finishing, and feeds synthesis gas and carries out the CO hydrogenation reaction, H in the synthesis gas
2With the volume ratio of CO be 2: 1, flow is 60mL/min, adjusts reaction pressure simultaneously to 2MPa, adopts gas-chromatography that product is carried out on-line analysis, product analysis shows, adopts with spherical hollow SiO
2The selectivity of the CO preparing methanol by hydrogenation of carrier-supported precious metal Pd reaches 100%, and the conversion per pass of CO reaches 8%, illustrates to adopt hollow SiO
2The eggshell type noble metal catalyst of carrier to load metal preparation can make the CO hydrogenation reaction, its conversion per pass and to adopt general silica gel be that the conversion ratio of noble metal catalyst of preparing carriers is suitable, but the selectivity of methyl alcohol is higher relatively.
Embodiment 14
Taking by weighing 0.5g is the eggshell type noble metal catalyst of co-catalyst by the load P dO of embodiment 4 preparation with alkaline-earth metal Ca, it is filled in volume is that 5mL, internal diameter are in the micro fixed-bed reactor of 10mm, adopting purity is that 99.999% High Purity Hydrogen is carried out hydrogen reducing, adopt temperature programming during reduction, heating rate is 2 ℃/min, reduction temperature is 400 ℃, hydrogen flowing quantity is 30mL/min, recovery time is 3h, can obtain through pretreated be the eggshell type precious metals palladium catalyst Ca-Pd/SiO of co-catalyst with alkaline-earth metal Ca
2Reduction cools the temperature to 220 ℃ after finishing, and feeds synthesis gas and carries out the CO hydrogenation reaction, H in the synthesis gas
2With the volume ratio of CO be 2: 1, flow is 60mL/min, adjusts reaction pressure simultaneously to 2MPa, adopts gas-chromatography that product is carried out on-line analysis, product analysis shows, adopts with hollow SiO
2Carrier is that the selectivity of CO hydrogenation reaction system methyl alcohol of the precious metals pd catalyst of co-catalyst reaches 100% with Ca, and the conversion per pass of CO reaches 15%, illustrates with spherical hollow SiO
2Be carrier, alkaline-earth metal Ca is that the eggshell type precious metals palladium catalyst of co-catalyst can make that the conversion per pass of CO hydrogenation reaction is higher, is the conversion ratio height of the noble metal catalyst of preparing carriers than adopting general silica gel, and the selectivity of methyl alcohol is higher relatively simultaneously.
Embodiment 15
Take by weighing the nickel-loaded-palladium egg-shell catalyst of 0.3g by embodiment 11 preparations, it is filled in volume is that 5mL, internal diameter are in the micro fixed-bed reactor of 10mm, adopting purity is that 99.999% High Purity Hydrogen is carried out hydrogen reducing, adopt temperature programming during reduction, heating rate is 2 ℃/min, and reduction temperature is 400 ℃, and hydrogen flowing quantity is 30mL/min, recovery time is 3h, can obtain through pretreated Ni-Pd/SiO
2Catalyst.Reduction cools the temperature to 220 ℃ after finishing, and feeds synthesis gas and carries out the CO hydrogenation reaction, H in the synthesis gas
2With the volume ratio of CO be 2: 1, flow is 60mL/min, adjusts reaction pressure simultaneously to 2MPa, adopts gas-chromatography that product is carried out on-line analysis, product analysis shows, adopts with hollow SiO
2The Ni-Pd catalyst of carrier, the selectivity of its CO hydrogenation reaction system methyl alcohol reaches 100%, and the conversion per pass of CO reaches 7%.
Embodiment 16
Take by weighing 0.3g nickel catalyst carried by embodiment 10 preparation, filling in volume is that 5mL, internal diameter are in the micro fixed-bed reactor of 10mm, adopting purity is that 99.999% High Purity Hydrogen is carried out hydrogen reducing, adopt temperature programming during reduction, heating rate is 2 ℃/min, reduction temperature is 400 ℃, and hydrogen flowing quantity is 30mL/min, and the recovery time is 3h.Reduction cools the temperature to 220 ℃ after finishing, and feeds synthesis gas (H
2With the volume ratio of CO be 2: 1), its flow is 60mL/min, adjusts reaction pressure simultaneously to 2MPa.Adopt gas-chromatography that product is carried out on-line analysis.Product analysis shows, adopts with hollow SiO
2Carrier to load metal nickel reaches 100% in the selectivity of CO preparing methanol by hydrogenation, and the conversion per pass of CO reaches 68%, illustrates to adopt hollow SiO
2The egg-shell catalyst of carrier to load metal preparation can make that the conversion per pass of CO hydrogenation reaction is higher.The conversion per pass of CO and the selectivity of methyl alcohol along with the variation in reaction time as shown in Figure 6.
Claims (10)
1. an egg shell type metal catalyst is made up of silica supports, noble metal and/or transition metal, selectable base metal co-catalyst, it is characterized in that wherein said carrier is the silica of hollow-core construction.
2. catalyst according to claim 1, it is characterized in that, with catalyst weight percentage is that the composition of benchmark comprises: 0.1%～5.0% noble metal and/or 5.0%～40.0% transition metal, 0～0.5% base metal co-catalyst, 60.0%～99.0% hollow silicon dioxide carrier.
3. catalyst according to claim 1 is characterized in that, wherein said carrier is spherical or tubulose, and the specific area of spherical hollow silicon dioxide particle is 500～1500m
2/ g, pore volume are 0.3～1.0mL/g; Tubular, hollow SiO
2The specific area of particle is 400～1000m
2/ g, pore volume are 0.3～1.0mL/g, and diameter is 80～150nm, and length is 1～3 μ m.
4. catalyst according to claim 3 is characterized in that, the specific area of wherein said spherical hollow silicon dioxide particle is 500～1000m
2/ g, pore volume are 0.5～0.9mL/g; Tubular, hollow SiO
2The specific area of particle is 500～800m
2/ g, pore volume are 0.5～0.8mL/g.
5. catalyst according to claim 1, it is characterized in that, wherein said noble metal is selected from one or more among Pd, Pt, the Rh, described transition metal is selected from one or more among Ni, Cu, the Zn, and described base metal co-catalyst is selected from one or more in alkali metal, alkaline-earth metal, group vib element and other transition metal.
6. the preparation method of an egg shell type metal catalyst is characterized in that, this method in turn includes the following steps:
The hollow silicon dioxide carrier is joined in acetate, nitrate, sulfate or the halid solution of at least a noble metal and/or at least a transition metal, and fully mix with it, temperature is controlled at 20～80 ℃; Load is filtered after finishing, and is warmed up to 80～130 ℃ with 10～20 ℃/min, dry 3～15h; With dried powder screening, be warmed up to 400～500 ℃ with 1～5 ℃/min at last, calcining 3～12h.
7. the preparation method of an egg shell type metal catalyst is characterized in that, this method in turn includes the following steps:
Adopt polymethyl methacrylate to make organic formwork, ethyl orthosilicate is the silicon source, the acetate of at least a noble metal and/or at least a transition metal, nitrate, sulfate or halide are presoma, with the corresponding acid of halide or salt be hydrolytic reagent and precipitating reagent, control pH value is between 1～3, and hydrolysis 10～20h is to the solution clear; Filter, be warmed up to 95～115 ℃ with 10～20 ℃/min then, dry 5～10h; With dried powder screening, be warmed up to 400～600 ℃ with 1～5 ℃/min at last, calcining 3～7h.
8. the preparation method of an egg shell type metal catalyst is characterized in that, this method in turn includes the following steps:
Acetate, nitrate, sulfate or the halid solution of transition metal are joined hollow SiO
2In the colloidal solution of carrier, and fully stir with it, drip simultaneously and be selected from Na
2CO
3, NaCHO
3Perhaps NH
3HCO
3Precipitating reagent, mixing speed is controlled at 400～600r/min, the pH value of maintenance system is between 8～10, mixing time is 12～24h; Load is filtered after finishing, and is warmed up to 90～110 ℃ with 10～20 ℃/min then, dry 3～12h; Dried powder sieves with standard screen, and the powder after the screening is carried out calcination processing, and calcining heat is 450～500 ℃, and heating rate is 1～5 ℃/min, and calcination time is 3～10h.
9. the preparation method of an egg shell type metal catalyst is characterized in that, this method in turn includes the following steps:
To further join in the solution of non-noble metal halide, nitrate or carbonate according to claim 6 or 7 or 8 catalyst that make, and fully mix with it, temperature is controlled at 20～80 ℃; Load is filtered after finishing, and is warmed up to 90～110 ℃ with 10～20 ℃/min, dry 3～12h; With dried powder screening, be warmed up to 400～450 ℃ with 1～5 ℃/min at last, calcining 3～10h.
10. the application of the catalyst of each of claim 1～5 in co hydrogenation system methyl alcohol.
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