CN109847737A - A kind of preparation method of supported nano-catalyst - Google Patents
A kind of preparation method of supported nano-catalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011943 nanocatalyst Substances 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 47
- 230000032683 aging Effects 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 abstract description 7
- 239000000470 constituent Substances 0.000 abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- 239000010931 gold Substances 0.000 description 20
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229940018564 m-phenylenediamine Drugs 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 3
- 229910001630 radium chloride Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229910000636 Ce alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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Abstract
A kind of preparation method of carrier nanometer catalyst, it is characterized by: the metal active constituent that the catalyst contains composite oxide carrier and is supported on carrier, the composite oxide carrier is SiO2-MOx (M Zr, Ce or La), by the amount ratio of atom species, Si:M 100:1-20；The metal active constituent is one of Pd, Pt, Rh, Au, and on the basis of the total amount of catalyst, by weight content meter, and metal active constituent content is 0.1-5%, remaining as carrier.It compares with other methods, catalyst prepared by the present invention active component high uniformity dispersion, has many advantages, such as the mesoporous of rule and narrow pore-size distribution at large specific surface area, and preparation method is simple, it is easy to accomplish industrialization.
Description
Technical field
The present invention relates to a kind of preparation methods of carrier nanometer catalyst, and in particular, to a kind of collosol and gel legal system
The method of standby carrier nanometer catalyst.
Background technique
Loaded catalyst includes two elements of active component and carrier, and certain loaded catalysts further include
Aid Portions.Carrier refers to the substance for supporting active component and auxiliary agent.Therefore, carrier needs to have enough mechanical strengths, and
And usually porous material, to be dispersed in active component and auxiliary agent above.
Oxide is common catalyst carrier.In general, oxide carrier can increase catalyst activity component with
The contact area of reactant, so that the yield of product be made to improve.Common catalyst carrier have aluminium oxide, silica, magnesia,
The oxide carriers such as titanium oxide.Different carriers have Different Effects, and the oxide carrier and difference of catalyst to differential responses
Catalyst metal components action modes it is different, will result directly in has completely different influence to catalyst performance.And work as carrier
Middle Multiple components are compound, and more excellent performance may be implemented.The property of complex carrier depends not only on the property of single component,
It is more dependent upon the pattern of two-phase and the active force between them.Although composite oxides and two or more components is compound,
But due to there are stronger active force or foring interpenetrating networks between the component of composition material, the size of microcell is usually in nanometer
Grade, even up to molecular level sometimes, so the composite oxides formed are very uniform in whole system.In addition, multiple
The property for closing oxide is also not the simple adduction of constituent component property, usually shows excellent not available for many one-components
Benign energy.For example, the SiO with high-ratio surface and structural stability2-Al2O3Complex carrier, it is net in petrochemical industry, vehicle exhaust
There is extensive purposes in the fields such as change, the conversion of NOx.SiO2-Al2O3Composite oxides have very high specific surface, dispersion degree
It is good, and performance is stablized when high-temperature roasting, can be used as the carrier of high temperature reaction catalyst.
SiO2-ZrO2Composite oxides also have many excellent physical and chemical performances, such as good mechanical strength, more by force
Surface acidity and catalytic activity, high thermal stability and chemical stability and ionic conductivity are good etc., thus answered extensively
For in many fields, especially ceramic modified, solid super-strong acid, inorganic separating film and in terms of.At present,
Have much about SiO2-ZrO2The report of composite oxides preparation and application aspect.SiO2-ZrO2Composite oxides are as excellent
Catalyst carrier also widely applied.Damyanova et al. (Damyanova S., Petrov L., Centeno
M.A., etc, Applied Catalysis A:General, 2002,224 (l-2), 271-284) have studied SiO2-ZrO2It is compound
The Hydrobon catalyst of oxide carried Mo is found in SiO2A small amount of ZrO is added in carrier2, can greatly change surface Mo
The dispersion degree of oxide, and then improve the reactivity of catalyst.Rana et al. (Rana M.S., Srinivas B.N.,
Maity S.K., etc., Journal of Catalysis, 2000,195 (1), 31-37) have studied SiO2-ZrO2Load
Catalytic activity of Mo, CoMo and NiMo catalyst in cumene hydrocracking reaction finds that Si content is higher in carrier
The activity of catalyst is more preferable, and the active promotion of the composite oxide supported catalyst to rich Si of auxiliary agent Co and Ni is made
With also becoming apparent.Chen et al. (Chen J.G.Xiang H.W., Gao H.Y., Reaction Kinetics and
Catalysis Letters, 2001,73 (1), 9) have studied SiO2-ZrO2The Co catalyst of load is in F-T synthetic reaction
Activity, activity is gradually reduced discovery catalyst during the reaction, and the catalyst after inactivation uses H2673K reduction can be
Activity recovery to a certain extent.
With SiO2、ZrO2、Al2O3Equal inert carriers are different, CeO2In cerium can lose two 6s electronics and a 5d electronics
Trivalent cerium ion is generated, the quadrivalent ion with stable 4f unoccupied orbital can also be formed.That is in the oxide of cerium,
The valence state of cerium can change under various circumstances, while this variation is reversible, CeO2This unique characteristic of appraising at the current rate,
Make it have good redox ability.Simultaneously because oxygen defect is rich in, when containing CeO in carrier2, point of noble metal component
Scattered property just will receive CeO2Influence so that the dispersibility of noble metal is more preferable, partial size is smaller.G Yi et al. (G Yi, H Yang, Y
Yuan,etc,Preferential co oxidation in a H2-rich gas by Au/CeO2
catalysts nanoscale CeO2shape effect and mechanism aspect.Catalysis
Today, 2010,157 (1-4): 83-88.) find that Au particle can be embedded in CeO2In carrier, or even at the oxygen defect of carrier
Au-Ce alloy is formed, this shows Au and CeO2Between have stronger interaction.Corma group (A Corma, ME
Domine.Gold supported on a mesoporous CeO2matrix as an efficient catalyst in
the selective aerobic oxidation of aldehydes in the liquid
Phase.Chem.Commun., 2005,0,4042-4044) use nano Ce O2Au is loaded, with high selectivity by aromatic alcohol and two
The monohydric alcohols such as grade fatty alcohol are oxidized to aldehydes or ketones.Campo et al. (B Campo, M Volpe, etc, Liquid phase
hydrogenation of crotonaldehyde over Au/CeO2catalysts.Applied Catalysis A:
General, 2009,359 (l-2), 79-83) report, Au/CeO2It with catalyzed gas crotonic acid hydrogenation reaction and can achieve
Higher selectivity.CeO2Composite inert oxide can obtain more excellent performance of catalyst.Y Xu et al. (Y Xu, C
Zhang,etc,Preferential co oxidation in a H2-rich gas by Au/CeO2catalysts
nanoscale CeO2shape effect an Synthesis of a hierarchical SiO2/Au/CeO2rod-like
nanostructure for high catalytic activity and recyclability.RSC Adv.,2015,5,
34549-34556) in Au/CeO2On the basis of wrapped up one layer of mesoporous silicon oxide and be prepared for using mesoporous silicon oxide as shell
Hud typed Au catalyst carrys out growing up for restricted activity gold particle, while mesoporous presence ensure that the fast of reactants and products
Speed diffusion.
And contain La in carrier2O3When, it can reduce the interaction force between active metal and carrier, inhibitory activity gold
Belong to particle growth, obtains more high degree of dispersion.For example, by step impregnation method, first in carrier S iO2Upper introducing La2O3, it is re-introduced into
Ni can largely weaken carrier S iO2With the interaction between nickel species, increase the nickel object for being easy to restore in catalyst
Kind quantity, and nickel crystal size is made to become smaller, dispersion degree increases, can be with when adding hydrogen m-phenylene diamine (MPD) for being catalyzed m-dinitrobenzene
M-dinitrobenzene conversion ratio and m-phenylene diamine (MPD) yield are improved simultaneously.
Composite oxides, which make catalyst carrier, can improve catalytic performance, but its effect is largely determined by its preparation
Method.Preparation method has coprecipitation, ion-exchange, infusion process and sol-gel method etc..But coprecipitation, ion
That there is specific surface areas and pore volume is smaller for exchange process and product prepared by infusion process, composition is not easy to control and less reproducible etc.
Disadvantage.Sol-gel rule can be by selecting reaction reagent, reaction condition and drying condition appropriate and rationally control reaction
Each step control catalyst microstructure.The advantages of this method is: the uniformity of product is high, and especially multi-component product is equal
Evenness can reach molecule or atomic level；Metal component is highly dispersed in carrier, and catalyst is enable to have high activity and anti-carbon
Power；The composition of material can relatively easily be controlled.Research finds the thermal stability of its structure of the catalyst of sol-gel method preparation
It is good, and the catalyst of the synthesis such as preparation method of the traditional loaded catalyst such as precipitation method, infusion process, ion-exchange is difficult
Meet the requirement of the anti-sintering under higher temperature reaction condition, therefore sol-gel method has attracted much attention in catalytic field.
Summary of the invention
The present inventor passes through a series of experiments and trial, ultimately provides a kind of easy-to-use solidifying using colloidal sol
The method of glue method synthesis carrier nanometer catalyst.Sol-gel method has method simple, it is not necessary to expensive device, active group
Point and carrier component can simultaneously in the solution mixing thus have the characteristics that solution reaction such as component is easy to modulation, between each component
The advantages that interspersed high is uniform.Sol-gel technology can synthesize the composite oxides of Large ratio surface, narrow pore-size distribution, and
Third component is easily introduced in the sol-gel process, and preparation condition has significant impact to the performance of composite oxides.
The present invention provides a kind of loaded catalysts, draw while using sol-gal process synthesizing composite oxide carrier
Enter metal active constituent, which contains SiO2-MOxIt (M Zr, Ce or La) composite oxide carrier and is supported on carrier
Metal active constituent (one of Pd, Pt, Rh, Au), by the amount ratio of atom species, Si:M 100:1-100:20；To urge
On the basis of the total amount of agent, the content of content meter by weight, active component is 0.1-5%, remaining as SiO2-MOx(M Zr, Ce
Or La) composite oxide carrier.
A kind of preparation method of loaded catalyst provided by the invention, comprising the following steps:
It 1, (is all polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer by a certain amount of P123 or F127
Object) it is dissolved in dehydrated alcohol, stir certain time；It is added after dissolution completely containing metal active constituent (in Pd, Pt, Rh, Au
One kind) soluble metal salt, continue to stir, obtain solution A；
2, a certain amount of ethyl orthosilicate is dissolved in dehydrated alcohol, stirs to get solution B；
3, by one of a certain amount of zirconium nitrate, cerous nitrate or lanthanum nitrate or it is two or more be dissolved in dehydrated alcohol,
Stir to get solution C；
4, continue to stir certain time after A, B, C solution mixing, then aging at a certain temperature is dry, and the dry of formation is coagulated
Glue obtains final catalyst in Muffle kiln roasting.
Perhaps the charge weight of F127 and dehydrated alcohol ratio is 1:6-16 P123 or F127 and Pd, Pt, Rh or Au to P123
Charge weight ratio be 400-2000:1.
Steps 1 and 2, in 3,4, stirring all carries out at room temperature.
In step 1, it is 2-5 hours that P123 or F127, which are dissolved in mixing time in dehydrated alcohol,；Be added containing Pd,
One of Pt, Rh or the salt of Au or more active metal, the time for continuing stirring is 0.5-2 hours.
In step 2, by weight, ethyl orthosilicate and dehydrated alcohol charge weight ratio are 1:3-10, and mixing time is
1.5-4 hour.
In step 3, by weight, one of zirconium nitrate, cerous nitrate or lanthanum nitrate or two or more and anhydrous second
Alcohol charge weight ratio is 1:3-20, and mixing time is 1.5-4 hours.
In step (4), the A, B, C solution are that 2-3:1:1 is mixed according to weight ratio.
In step 4, mixing time is 4-8 hours, and aging drying temperature is usually 40-80 DEG C, preferably 50-70 DEG C；Always
Changing drying time is usually 24-72 hours, preferably 36-60 hours；Aging drying can be air atmosphere；Maturing temperature is usual
It is 300-500 DEG C, calcining time is usually 3-5 hours, and calcination atmosphere is air atmosphere.
It compares with other methods, the active component high uniformity dispersion of catalyst prepared by the present invention, specific surface area
Greatly, have many advantages, such as the mesoporous of regular and narrow pore-size distribution, and preparation method is simple, it is easy to accomplish industrialization.
Specific embodiment
The present invention is further detailed below with reference to embodiment, but is not so limited the present invention.
In following embodiment, the drug of selection is all that analysis is pure.
Embodiment 1
Prepare Pd/SiO2-ZrO2Catalyst
2g P123 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；Four ammonium of 0.014g nitric acid is added after dissolution completely
Palladium continues stirring 1 hour；Obtain solution A.2.874g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, is stirred 2 hours,
Obtain solution B.0.592g zirconium nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.By A, B, C solution
Continue stirring 5 hours after mixing, be then transferred into 60 DEG C of baking ovens, aging is 48 hours dry.Obtained solid is ground with mortar
It clays into power, in Muffle furnace, setting Muffle furnace heating rate is 1 DEG C/min and rises to 400 DEG C by room temperature, in air atmosphere
Roasting 4 hours.Its BET measurement the specific area is 252m2/ g, pore-size distribution concentrate between 5-7nm；CO Pulse Chemisorption meter
It calculates the results show that its Pd dispersion degree is 75%.
Embodiment 2
Prepare Pt/SiO2-ZrO2Catalyst
2g F127 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.0136g chloroplatinic acid is added after dissolution completely,
Continue stirring 1 hour；Obtain solution A.2.874g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains
Solution B.0.592g zirconium nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.A, B, C solution are mixed
After continue stirring 5 hours, be then transferred into 50 DEG C of baking ovens, aging dry 72 hours.With mortar by obtained solid abrasive at
Powder, in Muffle furnace, setting Muffle furnace heating rate is 1 DEG C/min and rises to 500 DEG C by room temperature, roasts 4 in air atmosphere
Hour.Its BET measurement the specific area is 265m2/ g, pore-size distribution concentrate between 5-6nm；CO Pulse Chemisorption calculates knot
Fruit shows that Pt dispersion degree is 81%.
Embodiment 3
Prepare Rh/SiO2-ZrO2Catalyst
2g P123 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.025g radium chloride is added after dissolution completely, after
Continuous stirring 1 hour；Obtain solution A.2.874g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains molten
Liquid B.0.592g zirconium nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.After A, B, C solution are mixed
Continue stirring 5 hours, be then transferred into 50 DEG C of baking ovens, aging is 72 hours dry.With mortar by obtained solid abrasive at powder
End, in Muffle furnace, setting Muffle furnace heating rate is 1 DEG C/min and rises to 400 DEG C by room temperature.Roasting 4 is small in air atmosphere
When.Its BET measurement the specific area is 270m2/ g, pore-size distribution concentrate between 5-7nm；CO Pulse Chemisorption calculated result
It has been shown that, Pd dispersion degree are 79%.
Embodiment 4
Prepare Au/SiO2-ZrO2Catalyst
2g P123 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.021 gold chloride is added after dissolution completely, after
Continuous stirring 1 hour；Obtain solution A.2.874g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains molten
Liquid B.0.592g zirconium nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.After A, B, C solution are mixed
Continue stirring 5 hours, remaining aging drying, calcination steps are the same as embodiment 1.Its BET measurement the specific area is 262m2/ g, aperture
Distribution concentrates between 5-8nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 85%.
Embodiment 5
Prepare Pd/SiO2-CeO2Catalyst
2g P123 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；Four ammonium of 0.014g nitric acid is added after dissolution completely
Palladium continues stirring 1 hour；Obtain solution A.2.695g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, is stirred 2 hours,
Obtain solution B.0.562g cerous nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.By A, B, C solution
Continue stirring 5 hours after mixing, remaining aging drying, calcination steps are the same as embodiment 2.Its BET measurement the specific area is 275m2/
G, pore-size distribution concentrate between 5-7nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 84%.
Embodiment 6
Prepare Pt/SiO2-CeO2Catalyst
2g F127 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.0136g chloroplatinic acid is added after dissolution completely,
Continue stirring 1 hour；Obtain solution A.2.695g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains
Solution B.0.562g cerous nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.A, B, C solution are mixed
After continue stirring 5 hours, remaining aging is dry, calcination steps are the same as embodiment 3.Its BET measurement the specific area is 271m2/ g, hole
Diameter distribution concentrates between 5-7nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 77%.
Embodiment 7
Prepare Rh/SiO2-CeO2Catalyst
2g P123 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.025g radium chloride is added after dissolution completely, after
Continuous stirring 1 hour；Obtain solution A.2.695g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains molten
Liquid B.0.562g cerous nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.After A, B, C solution are mixed
Continue stirring 5 hours, remaining aging drying, calcination steps are the same as embodiment 1.Its BET measurement the specific area is 263m2/ g, aperture
Distribution concentrates between 5-7nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 82%.
Embodiment 8
Prepare Au/SiO2-CeO2Catalyst
2g P123 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.021 gold chloride is added after dissolution completely, after
Continuous stirring 1 hour；Obtain solution A.2.695g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains molten
Liquid B.0.562g cerous nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.After A, B, C solution are mixed
Continue stirring 5 hours, remaining aging drying, calcination steps are the same as embodiment 2.Its BET measurement the specific area is 256m2/ g, aperture
Distribution concentrates between 6-8nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 75%.
Embodiment 9
Prepare Pd/SiO2-La2O3Catalyst
2g F127 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；Four ammonium of 0.014g nitric acid is added after dissolution completely
Palladium continues stirring 1 hour；Obtain solution A.2.248g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, is stirred 2 hours,
Obtain solution B.0.467g lanthanum nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.By A, B, C solution
Continue stirring 5 hours after mixing, remaining aging drying, calcination steps are the same as embodiment 3.Its BET measurement the specific area is 254m2/
G, pore-size distribution concentrate between 5-7nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 74%.
Embodiment 10
Prepare Pt/SiO2-La2O3Catalyst
2g F127 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.0136g chloroplatinic acid is added after dissolution completely,
Continue stirring 1 hour；Obtain solution A.2.248g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains
Solution B.0.467g lanthanum nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.A, B, C solution are mixed
After continue stirring 5 hours, remaining aging is dry, calcination steps are the same as embodiment 1.Its BET measurement the specific area is 258m2/ g, hole
Diameter distribution concentrates between 5-7nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 78%.
Embodiment 11
Prepare Rh/SiO2-La2O3Catalyst
2g P123 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.025g radium chloride is added after dissolution completely, after
Continuous stirring 1 hour；Obtain solution A.2.248g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains molten
Liquid B.0.467g lanthanum nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.After A, B, C solution are mixed
Continue stirring 5 hours, remaining aging drying, calcination steps are the same as embodiment 2.Its BET measurement the specific area is 265m2/g, aperture
Distribution concentrates between 5-8nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 79%.
Embodiment 12
Prepare Au/SiO2-La2O3Catalyst
2g P123 is dissolved in 20ml dehydrated alcohol, is stirred 3 hours；0.021 gold chloride is added after dissolution completely, after
Continuous stirring 1 hour；Obtain solution A.2.248g ethyl orthosilicate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains molten
Liquid B.0.467g lanthanum nitrate is dissolved in 10ml dehydrated alcohol, stirs 2 hours, obtains solution C.After A, B, C solution are mixed
Continue stirring 5 hours, remaining aging drying, calcination steps are the same as embodiment 3.Its BET measurement the specific area is 268m2/ g, aperture
Distribution concentrates between 5-7nm；CO Pulse Chemisorption calculated result shows that Pd dispersion degree is 82%.
Claims (9)
1. a kind of preparation method of loaded catalyst, which is characterized in that method includes the following steps:
(1) it by polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 or F127, is dissolved in anhydrous
In ethyl alcohol, certain time is stirred；It is added after dissolution completely in the solubility salt of the active metal containing Pd, Pt, Rh or Au
One kind continues to stir, obtains solution A；
(2) ethyl orthosilicate is dissolved in dehydrated alcohol, continues to stir to get solution B；
(3) one or more of zirconium nitrate, cerous nitrate or lanthanum nitrate are dissolved in dehydrated alcohol, continue to stir to get
Solution C；
(4) continue to stir certain time after mixing A, B, C solution, then aging at a certain temperature is dry, and the dry of formation is coagulated
Glue obtains final catalyst in Muffle kiln roasting.
2. according to the method described in claim 1, it is characterized by: wherein in step (1), by weight, P123 or F127
Charge weight ratio with dehydrated alcohol is 1:6-16.
3. according to the method described in claim 1, it is characterized by: wherein in step (1), by weight, P123 or F127
Charge weight ratio with Pd, Pt, Rh or Au is 400-2000:1.
4. according to the method described in claim 1, it is characterized by: stirring wherein in step (1) (2) (3) (4) all in room temperature
Under the conditions of carry out.
5. according to the method described in claim 1, it is characterized by: P123 or F127 are wherein dissolved in nothing in step (1)
Mixing time is 2-5 hours in water-ethanol；It is added containing after one of Pd, Pt, Rh or Au or more active metal salt, continues
The time of stirring is 0.5-2 hours.
6. according to the method described in claim 1, it is characterized by: wherein in step (2), by weight, ethyl orthosilicate with
Dehydrated alcohol charge weight ratio is 1:3-10, and mixing time is 1.5-4 hours.
7. according to the method described in claim 1, it is characterized by: wherein in step (3), by weight, zirconium nitrate, cerous nitrate
Either one of lanthanum nitrate or two or more and dehydrated alcohol charge weight ratio are 1:3-20, and mixing time is that 1.5-4 is small
When.
8. according to the method described in claim 1, it is characterized by: the A, B, C solution are according to weight wherein in step (4)
Than being mixed for 2-3:1:1.
9. according to the method described in claim 1, it is characterized by: mixing time is 4-8 hours, aging wherein in step (4)
Drying temperature is 40-80 DEG C, and preferably 50-70 DEG C, aging drying time is 24-72 hours, preferably 36-60 hours, is roasted
Temperature is 300-500 DEG C, and calcining time is 3-5 hours.
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