CN107537478A - A kind of self-supporting catalyst with core-casing structure and its preparation method and application - Google Patents

Abstract

The invention discloses a kind of self-supporting metal or metal oxide catalyst with core-casing structure, has below formula：XM yMO zShell/mAlO/ZT, quality composition：X is that 0~5%, y is that 0~10%, z is that 0.5~20%, m is 0.1~20%, surplus ZT.Described self-supporting metal or metal oxide catalyst with core-casing structure is made by the following method：1. carrying out hydro-thermal process and/or heat treatment to ZT in the aqueous solution of pure water or containing a source of aluminum and alkali source, self-supporting AlO/ZT complex carriers are made；2. the organic solution containing at least one metal M ion being coordinated with coupling agent impregnates obtained AlO/ZT carriers, by drying, being calcined and reduce, described self-supporting metal or metal oxide catalyst with core-casing structure is made.Self-supporting metal or oxide core shell structure catalyst provided by the invention can be used for low-concentration methane and VOC (VOCs) catalytic oxidation, catalyzing carbon monoxide oxidation reaction, preparing low-carbon olefin (FTO), methane to convert in the reaction of preparing synthetic gas.

Description

A kind of self-supporting core-shell structure catalyst and its preparation method and application

Technical field

The present invention relates to a kind of self-supporting metal or oxide core-shell structure catalyst and its preparation method and application, category In catalysis technical field.

Background technology

In the production of petroleum refining, petrochemical and fine chemicals, waste gas purification and renewable and clean energy resource In production process, metal nanoparticle catalyst is all inevitably used.Bulk effect, surface possessed by nano particle Effect, quantum size effect and macro quanta tunnel effect so that nanometer urges the catalytic activity of this agent and selectivity to be significantly larger than Traditional catalyst, such as aoxidized with gold nano catalyst catalysis CO of the particle diameter less than 2 nanometers, CO can be turned completely under room temperature condition Change (gas chemical industry, 2009,34 (3)：72-78)；It is hydrogenated with by the use of the nickel nanometer catalyst that particle diameter is 30 nanometers as cyclo-octadiene The catalyst of cyclo-octene reaction is generated, it is selectively 5~10 times of the Raney Raney nickels used now, and activity is its 2 ~7 times of (petrochemical industry, 1991,20 (9)：633-639).People are by controlling particle size and shape, the electronics for regulating and controlling metal The methods of interphase interaction of state and Metal-Support, to obtain more effective metal nano catalyst, this also causes metal to be received The design of rice grain becomes suitable elaborate.Interacted for Metal-Support, carrier is generally determining metal nanoparticle Catalytic performance in terms of play vital effect.However, the active periphery site at Metal-Support interface is in all metal watchs The ratio very little occupied in the site of face, cause active site insufficient.Meanwhile Metal-Support interaction can react Died down in journey, and then trigger the agglomeration traits of reactive nanoparticles.

By the use of carrier as shell come wrap up active metal nano particle prepare core-shell structure metall nanoparticles be it is a kind of very It is hopeful the scheme for solving above-mentioned Metal-Support interface problem.The structure of core-shell structure metall nanoparticles enables to metal Active interface area between (core) and carrier (shell) maximizes, and by shell come protection activity metal (core) from sintering. In past last decade, core-shell structure copolymer metal nanoparticle has been widely studied, such as modularization core-shell structure copolymer Pd@CeO₂It is nano combined Thing can significantly increase interfacial interaction, and show excellent activity and stability in methane catalytic combustion reaction and resist Sintering character (Science, 2012,337,713-717).However, increasingly accurately set with to core-shell structure copolymer metal nanoparticle Meter, its preparation process become quite cumbersome, it is often necessary to many steps and special process.These well-designed step limitations The extensive use and large-scale production of core-shell structure copolymer metal nanoparticle.Meanwhile existing core-shell structure copolymer metal nanoparticle prepares skill Art also only resides within laboratory stage, the Catalyat Engideering (such as shaping of catalyst) faced when expanding to production scale The understanding wretched insufficiency of engineering technology problem.

With expanding economy and the progress of society, the industry such as calcined ore, generating, the thousands of chemical substance of synthesis Activity, the concentration of some pernicious gases in air is set even to increase to hundred times at double, atmosphere pollution at present turns into facing mankind Most one of Tough questions.Research shows, the increase of pollutant, can not only trigger breathing problem, the heart of people Disease and cause death, can also make animals and plants by different degrees of injury so that destroy the ecosystem and mankind's normal existence and The condition of development.The extent of injury of atmosphere pollution occupy first of other environmental pollutions, turn into the rapid major issue to be solved it One.CO catalytic oxidation and unburned hydro carbons and its derivative (including low-concentration methane and volatile organic matter) are after mitigating discharge A kind of important supplement instrument of atmosphere pollution, and make full use of the energy and accomplish the effective way of pernicious gas zero-emission. However, low temperature high activity, high flux low pressure drop, anti-harsh thermal shock and service life length and the new height prepared suitable for modularization The research and development of CO catalytic oxidation and the catalyst and reactor technology of unburned hydro carbons and its derivative are imitated, are still that current environment is urged The challenging hot subject in change field.

On the other hand, world population is being continuously increased, increasingly increased energy consumption and limited non-renewable fossil fuel Contradiction is inevitably resulted between the reduction increasingly of resource.In order to reduce the dependence to oil, realize that the mankind's is sustainable Development, researcher couple utilizes with the variation for the fossil energy that efficient catalytic process is combined has rekindled keen interest. It is contemplated that as Coal Gasification prepares the huge advance of synthesis gas, F- T synthesis will turn into most strong in energy market Competitor, because it is liquid cleaning fuel and the pass that industrial chemicals is prepared by polymerization reaction on the solid surface that this, which is syngas catalytic conversion, Key step.Verified, some transition metal can be catalyzed fischer-tropsch reaction progress, and wherein Co, Fe and Ru show best reaction Activity.Because this is a heterogeneous catalysis process, the size and structure of active phase are to influence fischer-tropsch reaction catalytic performance very One of important factor.The dimensional effect of Co bases and Fe base catalyst has been widely studied, it was demonstrated that dimensional effect can be to activity Deep effect is caused with selectivity.Therefore, effective method is explored to control load type metal or metal oxide particle The catalyst of nucleation and growth, final design size and structure-controllable is for developing high performance industrial fischer-tropsch reaction catalyst extremely Close important.

Structure catalyst and reactor (Structured Catalyst and Reactor, SCR), it is big empty due to that can incite somebody to action Gap rate, small yardstick (particle), loose structure, bigger serface, thermal conductive resin and form factor of permeability and uniqueness etc. Be advantageous to improve reaction bed flowing it is integrated with heat/lot of essential factors such as matter transmission and geometric configuration flexible design, and by To increasing concern, in particular environmental catalysis (such as CO and the catalytic eliminating of unburned hydro carbons and its derivative) requires high pass The solution of the problems such as amount, low pressure drop provides new technological approaches.Strengthen mass transfer possessed by structure catalyst simultaneously and narrow The unique advantage of residence time destribution, the selectivity of FTO processes can be significantly improved.Therefore, how to provide with high flux, height The monolithic construction catalyst of heat and mass ability, by core-shell structure copolymer metal nanoparticle simply and efficiently, structure snd size it is controllable Ground loads to the surface of structure carrier, realizes grand that-micro--receive designs synthesis across the step of yardstick one, the heat transfer strengthened in course of reaction passes Matter, it is vital in the engineering issues for solve core-shell structure copolymer metal nanoparticle catalyst.

The content of the invention

It is an object of the invention to provide a kind of grand it is-micro--receive across the step of yardstick one design synthesis self-supporting metal or metal oxygen Compound core-shell structure catalyst and its preparation method and application.

The first aspect of the present invention, there is provided a kind of self-supporting metal or metal oxide core-shell structure catalyst, have Below formula：XM-yMO@zShell/mAlO/ZT, wherein xM-yMO@zShell represent metal and metal oxide is core, oxidation The nucleocapsid structure that thing or carbon are made up of shell, ZT represent the metal phase skeleton with porosity characteristic, and x represents that M is catalyzed in integrated Shared mass percent in agent, y represent MO mass percents shared in integrated catalyst, and z represents Shell self-contained Shared mass percent in formula catalyst, m represent AlO mass percents shared in integrated catalyst；And x be 0~ 5%, y are that 0~10%, z is that 0.5~20%, m is 0.1~20%, and surplus is the mass percent shared by metal phase skeleton ZT.

As a kind of preferred scheme, x preferred scopes are 0.2~4.0%；Y preferred scopes are 2~8%；Z preferred scopes are 1 ~10%, surplus is the mass percent shared by metal phase skeleton ZT.

As a kind of preferred scheme, described M in the transition metal such as gold, silver, platinum, ruthenium, palladium, rhodium, nickel, copper at least It is a kind of；Described MO in alkaline-earth metal, lanthanide rare metal, boron, aluminium, gallium, titanium, zirconium, zinc, Mn oxide at least one Kind；Described Shell is relevant with the product of roasting of coupling agent, is silicon, aluminium, rare earth, tin, phosphorus, boron, zirconium and titanyl compound and carbon At least one of material；The material of the ZT is in the metals such as nickel, copper, aluminium, iron, stainless steel, ferrum-chromium-aluminum, copper-nickel alloy, brass Any one；

As a kind of preferred scheme, M, MO, Shell and ZT of this catalyst can be selected from the material by including, But be not limited only to the material included, the similar such as of the same clan, homology of property, same type, metal simple-substance alloy can also conduct Present disclosure.

As further preferred scheme, described metal core is preferably at least one in Pd, Pt, Au, Ag, Fe, Co, Ni Kind；Metal oxide core is preferably at least one of cerium, lanthanum, gallium, titanium, zirconium, magnesium, calcium, manganese, potassium oxide.

As entering a kind of preferred scheme, described ZT metal phase carrier mediums preferably be selected from aluminium, copper, nickel, copper-nickel alloy, stainless steel, One kind in ferrum-chromium-aluminum；As another preferred scheme, the feature of described siderochrome alumina supporter is：The mass ratio of aluminium be 2~ 10%, the mass ratio of chromium is 10~30%.

As still more preferably scheme, a kind of self-supporting metal or metal oxide core-shell structure catalyst, it is xPd-yCeO₂@zSiO₂/mAl₂O₃/ ZT, wherein x are that 0.2~2%, y is that 0~5%, z is that 1~8%, m is 1~10%.

As still more preferably scheme, a kind of self-supporting metal or metal oxide core-shell structure catalyst, it is xAu-yFe₂O₃@zSiO₂/mAl₂O₃/ ZT, wherein x are that 0.2~1.5%, y is that 0~5%, z is that 1~8%, m is 2~10%.

As still more preferably scheme, a kind of self-supporting metal or metal oxide core-shell structure catalyst, it is xNi-yCeO₂@zSiO₂/mAl₂O₃/ ZT, wherein x are that 0.5~5%, y is that 0~5%, z is that 1~8%, m is 2~10%.

As still more preferably scheme, a kind of self-supporting metal or metal oxide core-shell structure catalyst, it is xAg-yFe₂O₃@z Al₂O₃/mAl₂O₃/ ZT, wherein x are that 0.2~2%, y is that 0~5%, z+m is 10~20%.

As another preferred scheme, the ZT is a diameter of 4~150 microns of fiber or formed by the fiber sintering Monoblock type metallic fiber with three-dimensional porous structure.Or the ZT is foam metal, wire netting, wire, sheet metal Or one or more combinations in tubular metal.

As further preferred scheme, the hole of described self-supporting metal or metal oxide core-shell structure catalyst Rate is 60~98%.

The second aspect of the present invention, there is provided one kind prepares above-mentioned self-supporting metal or metal oxide core-shell structure and urged The method of agent, comprises the following steps：

A) first with acid or alkali to metal phase (or nonmetallic phase) skeleton ZT processing, then ZT is put into pure water or contained Hydro-thermal process and/or heat treatment are carried out at a certain temperature in the stainless steel water heating kettle of silicon source and the alkali source aqueous solution, are down to room temperature Sample is cleaned and dried afterwards, realizes boehmite AlOOH nanometer sheets or Al₂O₃Anchor of the nanometer sheet on ZT surfaces is grown nonparasitically upon another plant It is long, self-supporting AlO/ZT complex carriers are made；

B) organic solution containing at least one metal M ion being coordinated with coupling agent impregnates obtained AlO/ZT carriers, After coupling agent is carried out spontaneous polycondensation with the surface hydroxyl in AlO/ZT carriers, by drying, being calcined and/or reduce, it is made described Self-supporting metal or metal oxide core-shell structure catalyst, be designated as：xM-yMO@zShell/mAlO/ZT.

As further preferred scheme, acid or alkali process in step a) are that metal phase skeleton ZT is put into acid or aqueous slkali In, handled at room temperature~60 DEG C.Described acid is preferably inorganic acid, such as：Hydrochloric acid；Described alkali is preferably inorganic Alkali, such as：Sodium hydroxide.

Silicon source described in step a) is sodium metaaluminate, aluminum nitrate, aluminum sulfate and aluminium chloride；The alkali source is urea, hydrogen-oxygen Change sodium, sodium carbonate and sodium acid carbonate.

Hydro-thermal process temperature in step a) is 80~300 DEG C, and hydrothermal conditions are 0.5~100 hour.

As further preferred scheme, coupling agent described in step b) is silane coupler, titanate coupling agent, Aluminate Coupling agent, bimetallic coupling agent, phosphate coupling agent, zirconium ester coupling agent, stannic acid ester coupling agent, boric acid ester coupler and wooden At least one of plain coupling agent.

Organic solution described in step b) is alcoholic solution, ketone solution, ethereal solution and toluene solution etc..

Sintering temperature in step b) is 200~600 DEG C, calcination atmosphere be air or high-purity protective atmosphere (such as：Purity Nitrogen, hydrogen, argon or helium atmosphere equal to or higher than 99.999%).

Self-supporting metal or oxide core-shell structure catalyst of the present invention can be applied to low-concentration methane and VOCs In catalytic oxidation and CO catalytic oxidations, it can also be applied in FTO reactions.

Compared with prior art, self-supporting metal or oxide core-shell structure catalyst provided by the invention are in performance With nanoparticle size and overall structure be controllable, the anti-sintering of Stability Analysis of Structures, Metal-Support interaction are strong, mass-and heat-transfer Can be good, permeability is high the advantages that, have the advantages that to be easy to be molded in use, be easy to filling, be easily stored, and its preparation method Simply, raw material is easy to get, beneficial to large-scale production；Can meet simultaneously strong suction/exothermic reaction in chemical field to flash heat transfer and The requirement of catalyst economics, can be for low-concentration methane and VOCs catalysis oxidations, CO catalysis oxidations, FTO reactions, methane The suitable catalyst of preparing synthetic gas is converted, there is conspicuousness industrial application value.

Brief description of the drawings

Fig. 1 is self-supporting core-shell structure catalyst prepared by embodiment 1：1Pd@1.5SiO₂/6Al₂O₃/ Ni-foam X- X ray diffration pattern x；

Fig. 2 is self-supporting core-shell structure catalyst prepared by embodiment 2：0.5Pd-2.5CeO₂@3.2SiO₂/6Al₂O₃/ Ni-foam x-ray diffraction pattern；

Fig. 3 is that the optical photograph of self-supporting AlOOH/Al50-SMF complex carriers prepared by the step 1 of embodiment 3 and SEM shine Piece；

Fig. 4 is the high power SEM photograph of self-supporting AlOOH/Al50-SMF complex carriers prepared by the step 1 of embodiment 3；

Fig. 5 is self-supporting core-shell structure catalyst prepared by embodiment 3：0.4Pd@1.1SiO₂/10Al₂O₃/Al50-SMF High power SEM photograph；

Fig. 6 is self-supporting core-shell structure catalyst prepared by embodiment 3：0.4Pd@1.1SiO₂/10Al₂O₃/Al50-SMF X-ray diffraction pattern；

Fig. 7 is self-supporting core-shell structure catalyst prepared by embodiment 3：0.4Pd@1.1SiO₂/10Al₂O₃/Al50-SMF TEM photos；

Fig. 8 is 0.4Pd@1.1SiO prepared by embodiment 3₂/10Al₂O₃/ Al50-SMF catalyst chloroazotic acid is molten to remove Pd@ SiO₂Remaining nano-pore SiO after Pd nano particles in nucleocapsid structure₂The TEM figures of shell；

Fig. 9 is 0.4Pd@1.0SiO prepared by embodiment 3₂/10Al₂O₃/ Al50-SMF catalyst is in CH₄Catalysis oxidation is anti- Catalytic performance in answering；

Figure 10 is the 0.4Pd@1.0SiO that methane concentration is prepared to embodiment 3₂/10Al₂O₃/ Al50-SMF catalyst is in CH₄ The influence of catalytic oxidation performance；

Figure 11 is 1Pd@1.5SiO prepared by embodiment 1₂/6Al₂O₃/ Ni-foam catalyst is in CH₄In catalytic oxidation Catalytic performance；

Figure 12 is 0.4Pd@1.0SiO prepared by embodiment 3₂/10Al₂O₃/ Al50-SMF catalyst is different in catalysis oxidation Catalytic performance in VOC reactions；

Figure 13 is 1Ag@13Al prepared by embodiment 6₂O₃/ Al80-fiber catalyst urging in CO catalytic oxidations Change performance；

Figure 14 is 1Au-2Fe prepared by embodiment 9₂O₃@6SiO₂/5Al₂O₃/ Ni-foam catalyst is anti-in CO catalysis oxidations Catalytic performance in answering；

Figure 15 is 0.4Pd@1.0SiO prepared by embodiment 3₂/10Al₂O₃/ Al50-SMF catalyst is in CH₄Catalysis oxidation is anti- Stability in answering；

Figure 16 is 0.4Pd/11Al prepared by comparative example₂O₃/ Al50-SMF catalyst is in CH₄It is steady in catalytic oxidation It is qualitative；

Figure 17 is 3Ni@5.4SiO made from embodiment 1₂/5Al₂O₃The methane dry gas of/FeCrAl-foam catalyst is reformed 200 hours stability results of catalytic reaction.

Embodiment

Technical scheme provided by the present invention, be to provide it is a kind of by anchor be attached to AlOOH on overall structure carrier (ZT) or Al₂O₃Nanometer sheet (AlO) carried metal (M) or metal oxide (MO) nucleocapsid structure and the catalyst formed, wherein so-called core- Shell structure is to represent metal and metal oxide by a kind of structure that core, oxide or carbon are that shell forms.

Nucleocapsid structure such as formula：XM-yMO@zShell, wherein x represent metal M matter shared in integrated catalyst Percentage is measured, y represents the oxide M O of of the same race or another metal mass percents shared in integrated catalyst, z tables Show Shell i.e. shell mass percent shared in integrated catalyst,

The ferrum-chromium-aluminum being previously mentioned in the present invention, i.e., general commercial ferrum-chromium-aluminum (FeCrAl) alloy.

A kind of self-supporting core-shell structure catalyst provided in the present invention, it is described in its carrier ZT morphosis The monoblock type metallic fiber with three-dimensional porous structure that fiber sintering forms can also be referred to as metal fiber felt or monoblock type Metal fiber felt.

Nanometer sheet carried metal or metal oxide core-shell structure and catalyst for being formed and preparation method thereof, and its Low-concentration methane and VOC (VOCs) catalytic oxidation, catalyzing carbon monoxide oxidation reaction and synthesis gas system Application in standby low-carbon alkene (FTO) reaction, realizes that successful anchor of the core-shell structure copolymer metal nanoparticle on overall structure carrier is attached, Solve the engineering issues of core-shell structure copolymer metal nanoparticle catalyst, to meet in environmental protection and chemical field to the height of catalyst The requirement of warm activity, high selectivity, high stability, high flux low pressure drop and augmentation of heat transfer, especially for low-concentration methane with VOCs catalytic oxidations, CO catalytic oxidations and FTO reactions provide a kind of preferable catalyst.

Technical scheme is furtherd elucidate with reference to embodiment and accompanying drawing：

Embodiment 1

1st, 5 grams of nickel foam is weighed, is handled 10 minutes with 1wt% dust technology, stainless steel water is put into after distilled water is cleaned In hot kettle, addition contains 0.714 gram of sodium metaaluminate (NaAlO₂) and 2.016 grams of urea (NH₂CONH₂) 70 milliliters of mixed solution, Hydro-thermal process 12 hours at 120 DEG C.It is repeatedly and dry with distillation water washing after being down to room temperature, obtain containing abundant surface hydroxyl Anchor tag shape boehmite self-supporting AlOOH/Ni-foam complex carriers；

2nd, 5 grams of self-supporting AlOOH/Ni-foam complex carriers made from step 1 are weighed, with the Pd (NO containing 0.05 gram of Pd₃)₂ With the acetone soln of 0.352 gram of γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), carry out waiting body at room temperature Product dipping 4 hours, after drying, it is calcined 2 hours in 550 DEG C in nitrogen, produces the attached γ-Al of anchor₂O₃Foam nickel carrier on load Pd@SiO₂Core-shell structure catalyst.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Pd matter Amount content is 0.95%, SiO₂Mass content be 1.51%, γ-Al₂O₃Mass content be 5.87%；Therefore, the present embodiment Prepared catalyst cartridge is designated as：1Pd@1.5SiO₂/6Al₂O₃/Ni-foam。

Learnt through macroscopic measurement：Self-supporting Pd@SiO prepared by this implementation₂Core-shell structure catalyst：1Pd@1.5SiO₂/ 6Al₂O₃/ Ni-foam porosity is 80%.

Fig. 1 is self-supporting Pd@SiO manufactured in the present embodiment₂Core-shell structure catalyst：1Pd@1.5SiO₂/6Al₂O₃/Ni- Foam x-ray diffraction pattern result, as seen from Figure 1：In addition to the diffraction maximum of metal phase carrier nickel, Pd diffraction is also detected that Peak, the particle size that Pd is calculated by Scherrer formula is 3.5 nanometers.

Nickel foam in the present embodiment is replaced with into foamed iron, resulting self-supporting Pd@SiO₂Core-shell structure catalyst It is abbreviated as：1Pd@1.4SiO₂/5Al₂O₃/Fe-foam。

Nickel foam in the present embodiment is replaced with into foam copper, 550 DEG C are calcined 2 hours in hydrogen atmosphere, resulting Self-supporting Pd@SiO₂Core-shell structure catalyst is abbreviated as：1Pd@1.7SiO₂/8Al₂O₃/Cu-foam。

Nickel foam in the present embodiment is replaced with into siderochrome aluminum foam, gained self-supporting AlOOH/FeCrAl-foam carriers 5 Gram with nickel acetylacetonate and the acetone soln of 1.01 grams of 3- aminopropyl triethoxysilanes (KH-550) containing 0.15 gram of Ni, in room Temperature is lower to carry out incipient impregnation 4 hours, after drying, is calcined 2 hours in 550 DEG C in nitrogen, produces self-supporting Ni@SiO₂Core- Shell structure catalyst is abbreviated as：3Ni@5.4SiO₂/5Al₂O₃/FeCrAl-foam。

Hydrothermal temperature in the present embodiment step 1 can be 140 DEG C or 180 DEG C, and hydrothermal conditions can be 1~2 Hour or 24 hours, remaining is identical with the present embodiment.

In the present embodiment step 2, used silane coupler can also be γ-(2.3 the third oxygen of epoxy) propyl group front three TMOS (KH-560), 3- aminopropyl triethoxysilanes (KH-550), N- aminoethyls-γ-aminopropyltrimethoxysilane Or 2- (3,4- 7-oxa-bicyclo[4.1.0s base) ethyl trimethoxy silane (KH-530) (KH792).

In the present embodiment step 2, used palladium precursor can also be palladium acetylacetonate, palladium, palladium bichloride and Ammonium chloropalladate.

If in the present embodiment step 2, with the Pd (NO containing 0.1 gram of Pd₃)₂It is isometric with 0.704 gram of KH570 acetone soln 5 grams of carriers are impregnated, carry out incipient impregnation 4 hours at room temperature, after drying, are calcined 2 hours in 550 DEG C in nitrogen, then institute Obtained self-supporting core-shell structure catalyst is abbreviated as：2Pd@3.2SiO₂/6Al₂O₃/Ni-foam。

Embodiment 2

1st, with the step 1 of embodiment 1；

2nd, 5 grams of self-supporting AlOOH/Ni-foam complex carriers made from step 1 are weighed, with the Pd containing 0.025 gram of Pd (NO₃)₂, 0.125 gram of CeO₂Ce (NO₃)₂With 0.717 gram of KH570 acetone soln, it is small that incipient impregnation 4 is carried out at room temperature When, after drying, it is calcined 2 hours in 550 DEG C in nitrogen, produces the attached γ-Al of anchor₂O₃Foam nickel carrier on load Pd-CeO₂@ SiO₂Core-shell structure catalyst.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In prepared catalyst, Pd mass content is 0.45%, CeO₂Mass content be 2.54%, SiO₂Mass content be 3.23%, Al₂O₃Mass content be 5.91%； Therefore, the catalyst cartridge prepared by the present embodiment is designated as：0.5Pd-2.5CeO₂@3.2SiO₂/6Al₂O₃/Ni-foam。

Learnt through macroscopic measurement：Self-supporting core-shell structure catalyst prepared by this implementation：0.5Pd-2.5CeO₂@ 3.2SiO₂/6Al₂O₃/ Ni-foam porosity is 80%.

Fig. 2 is self-supporting core-shell structure catalyst manufactured in the present embodiment：0.5Pd-2.5CeO₂@3.2SiO₂/6Al₂O₃/ Ni-foam x-ray diffraction pattern, it can be seen that：In addition to the diffraction maximum of metallic nickel, Pd and CeO is not detected by₂Diffraction maximum, can Energy reason is that the decentralization of both materials is high or load capacity is relatively low.

Embodiment 3

1st, sintering aluminum fiber (50 microns of fibre diameter) 5 grams of piece is weighed, is at 1wt% sodium hydrate aqueous solution with concentration Reason 10 minutes, it is put into after distilled water is cleaned in stainless steel water heating kettle, adds 70 milliliters of distilled water, the hydro-thermal process at 120 DEG C 12 hours.It is repeatedly and dry with distillation water washing after being down to room temperature, obtain the anchor tag shape containing abundant surface hydroxyl and intend thin water The self-supporting AlOOH/Al50-SMF complex carriers of aluminium stone；

2nd, 5 grams of self-supporting AlOOH/Al50-SMF complex carriers made from step 1 are weighed, with the Pd containing 0.025 gram of Pd (NO₃)₂With the acetone soln of 0.208 gram of Silane coupling agent KH550, incipient impregnation is carried out at room temperature 4 hours, after drying, It is calcined 2 hours in 550 DEG C in nitrogen, produces the attached γ-Al of anchor₂O₃Aluminum fiber supported on carriers Pd@SiO₂Nucleocapsid structure is catalyzed Agent.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Pd matter Amount content is 0.43%, SiO₂Mass content be 1.05%；The quality of sample before and after weighing hydro-thermal process during step 1 Difference, Al can be conversed₂O₃Mass content be 10%；Therefore, the catalyst cartridge prepared by the present embodiment is designated as：0.4Pd@ 1.1SiO₂/10Al₂O₃/Al50-SMF。

Learnt through macroscopic measurement：Self-supporting core-shell structure catalyst prepared by this implementation：0.4Pd@1.1SiO₂/ 10Al₂O₃/ Al50-SMF porosity is 85%.

Fig. 3 and Fig. 4 is the optical photograph for the self-supporting AlOOH/Al50-SMF complex carriers that the present embodiment step 1 is prepared And SEM photograph, it can be seen that form integrated structure after aluminum fiber sintering, and anchor is attached one layer on metal phase carrier aluminum fiber Uniform sheet boehmite.

Fig. 5 is self-supporting core-shell structure catalyst manufactured in the present embodiment：0.4Pd@1.1SiO₂/10Al₂O₃/Al50- SMF SEM photograph, it can be seen that the attached one layer of uniform silica of anchor in the honeycomb hole be made up of tabular alumina.

Fig. 6 is self-supporting core-shell structure catalyst manufactured in the present embodiment：0.4Pd@1.1SiO₂/10Al₂O₃/Al50- SMF x-ray diffraction pattern, as seen from Figure 6：In addition to the diffraction maximum of metallic aluminium, Pd diffraction maximum is not detected by, possible cause is The load capacity of palladium is relatively low.

Fig. 7 is self-supporting core-shell structure catalyst manufactured in the present embodiment：0.4Pd@1.1SiO₂/10Al₂O₃/Al50- SMF TEM photos, as seen from Figure 7：The particle size range of Pd particles is in 2-5 nanometers.

Fig. 8 is 0.4Pd@1.1SiO manufactured in the present embodiment₂/10Al₂O₃/ Al50-SMF catalyst chloroazotic acid is molten to remove Pd@ SiO₂Remaining nano-pore SiO after Pd nano particles in nucleocapsid structure₂The TEM figures of shell, it was demonstrated that Pd nano particles are certain It is embedded in SiO₂In shell.

If the present embodiment step 1, sintering aluminum fiber (50 microns of fibre diameter) 5 grams of piece, the hydrogen for being 1wt% with concentration are weighed Aqueous solution of sodium oxide is handled 10 minutes, is successively stacked to after distilled water is cleaned in quartz ampoule, water vapour is passed through at 120-600 DEG C 0.5-72h is handled, after being dried under nitrogen atmosphere, the anchor tag shape boehmite containing abundant surface hydroxyl can also be obtained Self-supporting AlOOH/Al50-SMF complex carriers.

If the present embodiment step 2, with the Pd (NO containing 0.05 gram of Pd₃)₂It is molten with the acetone of 0.416 gram of Silane coupling agent KH550 Liquid impregnates 5 grams of carriers, then resulting self-supporting core-shell structure catalyst is abbreviated as：0.9Pd@2.2SiO₂/10Al₂O₃/ Al50-SMF。

Embodiment 4

1st, with the step 1 of embodiment 3；

2nd, 5 grams of metal phase carrier made from step 1 are weighed, with containing 0.1 gram of Fe₂O₃Fe (NO₃)₃With 0.400 gram of broad-leaf forest The ethanol solution of lignin, carries out incipient impregnation 12 hours at room temperature, small in 500 DEG C of roastings 2 in hydrogen after drying When, produce the attached γ-Al of anchor₂O₃Aluminum fiber supported on carriers Fe₂O₃@C core-shell structure catalysts.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Fe₂O₃'s Mass content is 1.89%；Sample is of poor quality before and after weighing hydro-thermal process during step 1, can converse Al₂O₃Matter It is 10% to measure content；After the completion of step 2, according to the weight loss of thermogravimetric analysis, the mass content that carbon is calculated is 4.1%； Therefore, the catalyst cartridge prepared by the present embodiment is designated as：2Fe₂O₃@4C/10Al₂O₃/Al50-SMF。

Learnt through macroscopic measurement：Self-supporting core-shell structure catalyst prepared by this implementation：2Fe₂O₃@4C/10Al₂O₃/ Al50-SMF porosity is 87%.

If 0.1 gram of Fe will be contained in the present embodiment step 2₂O₃Fe (NO₃)₃It is molten with the ethanol of 0.400 gram of broad-leaf forest lignin Liquid, replace with containing 0.1 gram of Co₃O₄Acetylacetone cobalt and 0.500 gram of broad-leaf forest lignin ethanol solution, it is resulting from propping up Support Co₃O₄@C core-shell structure catalysts are abbreviated as：2Co₃O₄@5C/10Al₂O₃/Al50-SMF。

Embodiment 5

1st, a diameter of 8 microns, 5 grams of the nickel metallic fiber that length is 2~5 millimeters and the fibre that length is 0.1~1 millimeter are weighed 2.5 grams and 1.5 liters water of cellulose fiber are added in mixer, and paper machine is transferred to after being sufficiently stirred into dispersed fiber pulp It is interior, 8.5 liters are added water to, stirring, draining aftershaping；It is calcined 1 hour in 500 DEG C in air atmosphere after to be dried；Again in hydrogen In in 950 DEG C sinter 1 hour, by the thickness of product by suppress control at 1 millimeter, obtain sintering metal nickel fiber reinforcement, table It is shown as Ni8-SMF；

2nd, sintering metal nickel fiber reinforcement made from step 1 is cut into a diameter of 16 millimeters of disks and weighs 5 grams, use 1wt% dust technology is handled 5 minutes, is put into after distilled water is cleaned in stainless steel water heating kettle, add containing 0.855 gram of aluminum nitrate and 70 milliliters of the mixed solution of 3.562 grams of sodium carbonate, hydro-thermal process 24 hours at 140 DEG C.After being down to room temperature, with distillation water washing Repeatedly and dry, the self-supporting AlOOH/Ni8-SMF for obtaining the anchor tag shape boehmite containing abundant surface hydroxyl is compound Carrier；

3rd, 5 grams of self-supporting AlOOH/Ni8-SMF complex carriers made from step 2 are weighed, with the HAuCl containing 0.05 gram of Au₄ With the acetone soln of 0.589 gram of isopropyl three (positive ethylamino-ethylamino) titanate esters (KB-44), carry out at room temperature isometric Dipping 5 hours, after drying, it is calcined 5 hours in 500 DEG C in nitrogen, produces the attached γ-Al of anchor₂O₃Nickel fiber carrier on load Au@TiO2 nucleocapsid structure agents.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Au matter It is 2.34%, Al to measure the mass content that content is 0.91%, TiO2₂O₃Mass content be 7.29%；Therefore, the present embodiment institute The catalyst cartridge of preparation is designated as：0.9Au@2.3TiO2/7.3Al₂O₃/Ni8-SMF。

Learnt through macroscopic measurement：Self-supporting Au@TiO2 core-shell structure catalysts prepared by this implementation：0.9Au@ 2.3TiO2/7.3Al₂O₃/ Ni8-SMF porosity is 95%.

The diameter of nickel metallic fiber in the present embodiment step 1 is replaced with 4 microns, the roasting work after porous is handled Skill replaces with to be calcined 1 hour at 350 DEG C, and resulting self-supporting Au@TiO2 core-shell structure catalysts are abbreviated as：0.9Au@ 2.2TiO2/7.5Al₂O₃/Ni4-SMF。

The quality of aluminum nitrate and sodium carbonate in the present embodiment step 2 is replaced with into 1.283 grams and 5.343 grams, hydro-thermal respectively The condition of processing replaces with 120 DEG C of hydro-thermals 48 hours, and resulting self-supporting Au@TiO2 core-shell structure catalysts are abbreviated as： 0.9Au@2.3TiO2/12Al₂O₃/Ni8-SMF。

By in the present embodiment step 3, the Pd (NO for 5 grams of carriers of incipient impregnation₃)₂Au quality is replaced in the aqueous solution For 0.005 gram, 0.010 gram, 0.100 gram or 0.15 gram, KB-44 quality correspondingly replace with 0.059 gram, 0.118 gram, 1.178 Gram or 1.766 grams, resulting self-supporting Au@TiO2 core-shell structure catalysts are abbreviated as：0.1Au@0.2TiO2/7Al₂O₃/ Ni8-SMF, 0.2Au@0.5TiO2/7Al₂O₃/ Ni8-SMF, 2Au@4.2TiO2/7Al₂O₃/ Ni8-SMF and 3Au@6.1TiO2/ 7Al₂O₃/Ni8-SMF。

In the present embodiment step 3, used titanate coupling agent can also be (the dodecyl benzene sulfonyl of isopropyl three Base) titanate esters, (dioctylphosphato) metatitanic acid of isopropyl three fat, two (triethanolamine) metatitanic acid diisopropyl esters and two (levulinics Ketone group) metatitanic acid diisopropyl ester.

Sintering temperature in the present embodiment step 3 can be replaced 600 DEG C, and roasting time can be replaced 1~3 hour, roasting Atmosphere can be replaced air.

Embodiment 6

1st, 5 grams of aluminum fiber (80 microns of fibre diameter, long 5~10 millimeters), the sodium hydroxide for being 0.1wt% with concentration are weighed The aqueous solution is handled 10 minutes, is put into after distilled water is cleaned in stainless steel water heating kettle, 70 milliliters of distilled water is added, at 120 DEG C Hydro-thermal process 2 hours.It is repeatedly and dry with distillation water washing after being down to room temperature, obtain the anchor tag containing abundant surface hydroxyl The self-supporting AlOOH/Al80-fiber complex carriers of shape boehmite；

2nd, 5 grams of metal phase carrier made from step 1 are weighed, with the AgNO containing 0.01 gram of Ag₃With 0.763 gram of two (acetyl second Acetoacetic ester) aluminic acid diisopropyl ester acetone soln, carry out incipient impregnation 12 hours at room temperature, after drying, in hydrogen in 550 DEG C are calcined 2 hours, produce aluminum fiber supported on carriers Ag@Al₂O₃Core-shell structure catalyst.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Ag matter It is 0.17% to measure content；Scanned electro microscope energy spectrum analysis determines, in the catalyst prepared by the present embodiment, Al₂O₃Mass content For 10%；Therefore, the catalyst cartridge prepared by the present embodiment is designated as：0.2Ag@10Al₂O₃/Al80-fiber。

Learnt through macroscopic measurement：Self-supporting core-shell structure catalyst prepared by this implementation：0.2Ag@10Al₂O₃/Al80- Fiber porosity is 81%.

If the present embodiment step 2, with the AgNO containing 0.05 gram of Ag₃It is different with 3.815 gram of two (ethyl acetoacetate) aluminic acid two 5 grams of carriers of acetone soln incipient impregnation of propyl ester, then resulting self-supporting core-shell structure catalyst be abbreviated as：1Ag@ 13Al₂O₃/Al80-fiber。

In the present embodiment step 2, used aluminate coupling agent can also be isopropyl stearic acid oxygen base aluminum acid ester, Aluminate coupling agent (LD-B) and aluminate coupling agent (DL-411-A).

Embodiment 7

1st, 5 grams of aluminum fiber (150 microns of fibre diameter, long 10 millimeters), the sodium hydroxide water for being 0.1wt% with concentration are weighed Solution is handled 10 minutes, is put into after distilled water is cleaned in stainless steel water heating kettle, is added 70 milliliters of distilled water, the water at 120 DEG C Heat treatment 5 hours.It is repeatedly and dry with distillation water washing after being down to room temperature, obtain the anchor tag shape containing abundant surface hydroxyl The self-supporting AlOOH/Al150-fiber complex carriers of boehmite；

2nd, 5 grams of metal phase carrier made from step 1 are weighed, with the Pd (NO containing 0.025 gram of Pd₃)₂It is even with 0.350 gram of aluminium zirconium Join the ethanol solution of agent (TL-1), carry out incipient impregnation at room temperature 24 hours, after drying, 2 are calcined in 550 DEG C in nitrogen Hour, produce aluminum fiber supported on carriers Pd@ZrO₂-Al₂O₃Core-shell structure catalyst.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Pd matter Amount content is 0.45%, ZrO₂Mass content be 1.54%；Scanned electro microscope energy spectrum analysis measure, Al₂O₃Mass content be 10%；Therefore, the catalyst cartridge prepared by the present embodiment is designated as：0.5Pd@1.5ZrO₂-10Al₂O₃/Al150-fiber。

Learnt through macroscopic measurement：Self-supporting core-shell structure catalyst prepared by this implementation：0.5Pd@1.5ZrO₂- 10Al₂O₃/ Al150-fiber porosity is 80%.

If the present embodiment step 2, soaked in equal volume with the ethanol solution of H2PtCl6 and 0.350 gram of TL-1 containing 0.025 gram of Pt 5 grams of carriers of stain, then resulting self-supporting core-shell structure catalyst be abbreviated as：0.5Pt@1.5ZrO₂-10Al₂O₃/Al150- fiber。

If the present embodiment step 2, with the Pd (NO containing 0.025 gram of Pd₃)₂, 0.100 gram of CeO₂Ce (NO₃)₃With 1.000 grams TL-1 ethanol solution, 5 grams of carriers of incipient impregnation, then resulting self-supporting core-shell structure catalyst be abbreviated as：0.5Pd- 4CeO₂@4ZrO₂-12Al₂O₃/Al150-fiber。

In the present embodiment step 2, used aluminum-zirconium coupling agent can also be the aluminum-zirconium coupling agent (TL-2 of other TL series ~TL-5).

Embodiment 8

1st, 5 grams of nickel foam is weighed, is handled 10 minutes with 1wt% dust technology, stainless steel water is put into after distilled water is cleaned In hot kettle, addition contains 0.714 gram of sodium metaaluminate (NaAlO₂) and 2.016 grams of urea (NH₂CONH₂) 70 milliliters of mixed solution, Hydro-thermal process 12 hours at 160 DEG C.It is repeatedly and dry with distillation water washing after being down to room temperature, obtain containing abundant surface hydroxyl Anchor tag shape boehmite self-supporting AlOOH/Ni-foam complex carriers；

2nd, 5 grams of self-supporting AlOOH/Ni-foam complex carriers made from step 1 are weighed, with containing 0.1 gram of Fe₂O₃Fe (NO₃)₃, 0.05 gram of MnO₂Mn (NO₃)₂, 0.05 gram of K₂O KNO₃With 2.042 grams of KH550 ethanol solution, enter at room temperature Row incipient impregnation 12 hours, after drying, it is calcined 3 hours in 550 DEG C in nitrogen, produces the attached γ-Al of anchor₂O₃Nickel foam carry The integrated catalyst of nucleocapsid structure Fe-Mn-K composite oxides is loaded on body.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Fe₂O₃'s Mass content is 1.81%, MnO₂Mass content be 0.89%, K₂O mass content is 0.84%, SiO₂Mass content be 5.92%, Al₂O₃Mass content be 5.25%；Therefore, the catalyst cartridge prepared by the present embodiment is designated as：2Fe₂O₃-1MnO₂- 1K₂O@6SiO₂/5Al₂O₃/Ni-foam。

Learnt through macroscopic measurement：Self-supporting composite oxides core-shell structure catalyst prepared by this implementation：2Fe₂O₃- 1MnO₂-1K₂O@6SiO₂/5Al₂O₃/ Ni-foam porosity is 80%.

Embodiment 9

1st, with the step 1 of embodiment 8；

2nd, 5 grams of self-supporting AlOOH/Ni-foam complex carriers made from step 1 are weighed, with the HAuCl containing 0.05 gram of Au₄、 0.1 gram of Fe₂O₃Fe (NO₃)₃With 1.329 grams of KH550 ethanol solution, incipient impregnation is carried out at room temperature 24 hours, drying Afterwards, it is calcined 3 hours in 550 DEG C in nitrogen, produces the attached γ-Al of anchor₂O₃Foam nickel carrier on load Au-Fe₂O₃@SiO₂Core- Shell structure catalyst.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Au matter Amount content is 0.95%, Fe₂O₃Mass content be 1.88%, SiO₂Mass content be 6.25%, Al₂O₃Mass content be 5.28%；Therefore, the catalyst cartridge prepared by the present embodiment is designated as：1Au-2Fe₂O₃@6SiO₂/5Al₂O₃/Ni-foam。

Learnt through macroscopic measurement：Self-supporting core-shell structure catalyst prepared by this implementation：1Au-2Fe₂O₃@6SiO₂/ 5Al₂O₃/ Ni-foam porosity is 81%.

Embodiment 10

1st, foamed brass (50PPI is weighed；Ormolu) 5 grams, carry out taking out zinc with the aqueous hydrochloric acid solution that concentration is 10% anti- Answer 0.5 hour, be put into through distilled water flushing in stainless steel water heating kettle, addition contains 0.714 gram of sodium metaaluminate (NaAlO₂) and 2.016 Gram urea (NH₂CONH₂) 70 milliliters of mixed solution, hydro-thermal process 2 hours at 160 DEG C.After being down to room temperature, washed with distillation Wash multiple and dry, the self-supporting AlOOH/HT-foam for obtaining the anchor tag shape boehmite containing abundant surface hydroxyl is answered Close carrier；

2nd, 5 grams of metal phase carrier made from step 1 are weighed, with the Pd (NO containing 0.025 gram of Pd₃)₂, 0.05 gram of ZnO nitric acid The ethanol solution of zinc and 0.701 gram of ethyl acetoacetate diisopropyl Aluminate, carries out incipient impregnation 24 hours at room temperature, After drying, it is calcined 3 hours in 550 DEG C in atmosphere, produces foamed brass supported on carriers Pd-ZnO@Al₂O₃Nucleocapsid structure is urged Agent.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Pd matter It is 0.95%, Al to measure the mass content that content is 0.46%, ZnO₂O₃Mass content be 11.21%；Therefore, the present embodiment institute The catalyst cartridge of preparation is designated as：0.5Pd-1ZnO@11Al₂O₃/HT-foam。

Learnt through macroscopic measurement：Self-supporting core-shell structure catalyst prepared by this implementation：0.5Pd-1ZnO@11Al₂O₃/ HT-foam porosity is 84%.

Comparative example

1st, sintering aluminum fiber (50 microns of fibre diameter) 5 grams of piece is weighed, is at 1wt% sodium hydrate aqueous solution with concentration Reason 10 minutes, it is put into after distilled water is cleaned in stainless steel water heating kettle, adds 70 milliliters of distilled water, the hydro-thermal process at 120 DEG C 12 hours.It is repeatedly and dry with distillation water washing after being down to room temperature, obtain the anchor tag shape containing abundant surface hydroxyl and intend thin water The self-supporting AlOOH/Al50-SMF complex carriers of aluminium stone；

2nd, 5 grams of metal phase carrier made from step 1 are weighed, with the Pd (Ac) containing 0.025 gram of Pd₂Acetone soln, in room temperature Lower carry out incipient impregnation, after drying, it is calcined 2 hours in 400 DEG C in atmosphere, produces the attached γ-Al of anchor₂O₃Aluminum fiber carrier The integrated catalyst of upper supported palladium.

Learnt through inductively coupled plasma atomic emission spectrometry measure：In catalyst prepared by the present embodiment, Pd matter It is 0.44% to measure content；Sample is of poor quality before and after weighing hydro-thermal process during step 1, can converse Al₂O₃Quality Content is 11%；Therefore, the catalyst cartridge prepared by the present embodiment is designated as：0.4Pd/11Al₂O₃/Al50-SMF。

Learnt through macroscopic measurement：Catalyst prepared by this implementation：0.4Pd/11Al₂O₃/ Al50-SMF porosity is 84%.

Application examples 1

0.4Pd@1.0SiO prepared by embodiment 3 are investigated on fixed bed reactors₂/10Al₂O₃/ Al50-SMF catalyst In CH₄Catalytic performance in catalytic oxidation：Reactant is CH₄And air；Fixed bed reactors are that an internal diameter is 8 millimeters Quartz ampoule, unstripped gas mixed before reaction tube is entered, reacted after well mixed into beds.Reaction Product enters on-line chromatographic analysis, is analyzed using thermal conductivity cell detector (TCD).

Reaction condition：0.15 gram of catalyst amount, gas hourly space velocity 72000mLh^-1·g^-1, gas composition is in air CH containing 1vol%₄.Influence of the temperature to catalytic performance is investigated under these conditions, and experimental result is as shown in Figure 7.

As seen from Figure 9：With the rise of reaction temperature, CH₄Conversion ratio gradually rise, reach complete conversion at 390 DEG C.

The CH containing 1vol% in gas composition is air₄Under conditions of, investigate shadow of the gas hourly space velocity to catalytic performance Ring, experimental result is shown in Table 1.

Influence of the gas hourly space velocity of table 1 to catalytic performance

From table 1：At the same reaction temperature, with the increase of gas hourly space velocity, CH₄Conversion ratio gradually reduce.

Reaction condition：0.15 gram of catalyst amount, keep total gas couette constant, gas hourly space velocity 72000mLh^-1· g^-1, change CH₄Volume content, investigate CH₄Influence of the concentration to reactivity worth, experimental result is as shown in Figure 8.

As seen from Figure 10：At the same reaction temperature, with CH₄The increase of concentration, CH₄Conversion ratio gradually reduce.

Application examples 2

1Pd@1.5SiO prepared by embodiment 1 are investigated on fixed bed reactors₂/6Al₂O₃/ Ni-foam catalyst is in CH₄ Catalytic performance in catalytic oxidation：Reactant is CH₄And air；Fixed bed reactors are the stone that an internal diameter is 8 millimeters Ying Guan, unstripped gas are mixed before reaction tube is entered, and are reacted after well mixed into beds.Reaction product Into on-line chromatographic analysis, analyzed using thermal conductivity cell detector (TCD).

Reaction condition：0.15 gram of catalyst amount, gas hourly space velocity 72000mLh^-1·g^-1, gas composition is in air CH containing 1vol%₄.Influence of the temperature to catalytic performance is investigated under these conditions, and experimental result is as shown in Figure 11.

Application examples 3

0.4Pd@1.0SiO prepared by embodiment 3 are investigated on fixed bed reactors₂/10Al₂O₃/ Al50-SMF catalyst Catalytic performance in VOCs catalytic oxidations：Reactant is 1000ppm single VOC and air gaseous mixture；Fixed bed Reactor is the quartz ampoule that an internal diameter is 8 millimeters, and unstripped gas is mixed before reaction tube is entered, and is entered after well mixed Beds are reacted.Reaction product enters on-line chromatographic analysis, is analyzed using thermal conductivity cell detector (TCD).

Reaction condition：0.15 gram of catalyst amount, gas hourly space velocity 72000mLh^-1·g^-1, gas composition is in air Single VOC (such as methanol, formaldehyde, toluene, methyl formate, propylene) containing 1000ppm.Temperature pair is investigated under these conditions The influence of catalytic performance, experimental result is as shown in Figure 12.

Application examples 4

1Ag@13Al prepared by embodiment 6 are investigated on fixed bed reactors₂O₃/ Al80-fiber catalyst is catalyzed in CO Catalytic performance in oxidation reaction：Reactant is CO and air；Fixed bed reactors are the quartz ampoules that an internal diameter is 8 millimeters, Unstripped gas is mixed before reaction tube is entered, and is reacted after well mixed into beds.Reaction product enters On-line chromatographic analysis, analyzed using thermal conductivity cell detector (TCD).

Reaction condition：0.15 gram of catalyst amount, gas hourly space velocity 72000mLh^-1·g^-1, gas composition is in air CO containing 1vol%.Influence of the temperature to catalytic performance is investigated under these conditions, and experimental result is as shown in Figure 13.

Application examples 5

1Au-2Fe prepared by embodiment 9 is investigated on fixed bed reactors₂O₃@6SiO₂/5Al₂O₃/ Ni-foam catalyst Catalytic performance in CO catalytic oxidations：Reactant is CO and air；Fixed bed reactors are that an internal diameter is 8 millimeters Quartz ampoule, unstripped gas are mixed before reaction tube is entered, and are reacted after well mixed into beds.Reaction production Thing enters on-line chromatographic analysis, is analyzed using thermal conductivity cell detector (TCD).

Reaction condition：0.15 gram of catalyst amount, gas hourly space velocity 72000mLh^-1·g^-1, gas composition is in air CO containing 1vol%.Influence of the temperature to catalytic performance is investigated under these conditions, and experimental result is as shown in Figure 14.

Application examples 6

The catalyst of embodiment preparation is investigated on fixed bed reactors in CH₄Catalysis in catalytic oxidation is stable Property：Reactant is CH₄And air；Fixed bed reactors are that an internal diameter is 8 millimeters of quartz ampoule, and unstripped gas is into reaction tube Mixed, reacted after well mixed into beds before.Reaction product enters on-line chromatographic analysis, utilizes heat Pool detector (TCD) is led to be analyzed.

Reaction condition：0.15 gram of catalyst amount, gas composition is the CH containing 1vol% in air₄.In above-mentioned condition The lower 0.4Pd@1.0SiO for having investigated the preparation of embodiment 3₂/10Al₂O₃/ Al50-SMF catalysts CH₄The stabilization of oxidation reaction Property, experimental result is as shown in Figure 15.As can be seen that Pd@SiO₂Core-shell structure catalyst is in CH₄Shown in catalytic oxidation Excellent stability, it was confirmed that the excellent anti-sintering property of nucleocapsid structure.

Application examples 7

The 3Ni@5.4SiO of the preparation of embodiment 1 are investigated using fixed bed reactors₂/5Al₂O₃/ FeCrAl-foam catalyst Methane and CO 2 reformation preparing synthetic gas reaction (methane dry gas is reformed, DRM) catalytic performance, reaction raw materials be methane and Carbon dioxide (mol ratio 1:1.1).Fixed bed reactors are the quartz ampoules that an internal diameter is 16mm, and methane and carbon dioxide exists It is pre-mixed before into reaction tube, flowing through beds after well mixed is reacted.Reaction product condenses through cold-trap Gas-phase product enters chromatogram afterwards, is analyzed using thermal conductivity cell detector (TCD).Catalyst amount is 0.500g, used Reaction condition and corresponding conversion ratio are listed in table 2；800℃、5000h^-1Under gas hourly space velocity, the stability test result of 200 hours See Figure 17.

3Ni@5.4SiO made from the embodiment 1 of table 2₂/5Al₂O₃/ FeCrAl-foam methane dry gas Reforming catalyst performance

Application examples 8

The 3Ni@5.4SiO of the preparation of embodiment 1 are investigated using fixed bed reactors₂/5Al₂O₃/ FeCrAl-foam catalyst Methane portion oxidation synthesis gas catalytic performance, reaction raw materials are methane and oxygen (mol ratio 2:1).Fixed bed reactors It is that the quartz ampoule that an internal diameter is 6mm, methane and oxygen are pre-mixed before reaction tube is entered, flows through and urge after well mixed Agent bed is reacted.Reaction product enters chromatogram after cold-trap condenses, and is analyzed using thermal conductivity cell detector (TCD). Catalyst amount is 0.20g, and used reaction condition and corresponding conversion ratio are listed in table 3 with selectivity.

3Ni@5.4SiO made from the embodiment 1 of table 3₂/5Al₂O₃The methane portion oxidation catalysis of/FeCrAl-foam catalyst Performance

Contrast application examples

The catalyst of embodiment preparation is investigated on fixed bed reactors in CH₄Catalysis in catalytic oxidation is stable Property：Reactant is CH₄And air；Fixed bed reactors are that an internal diameter is 8 millimeters of quartz ampoule, and unstripped gas is into reaction tube Mixed, reacted after well mixed into beds before.Reaction product enters on-line chromatographic analysis, utilizes heat Pool detector (TCD) is led to be analyzed.

Reaction condition：0.15 gram of catalyst amount, gas composition is the CH containing 1vol% in air₄.In above-mentioned condition The lower 0.4Pd/11Al for having investigated comparative example preparation₂O₃/ Al50-SMF catalysts CH₄The stability of oxidation reaction, experiment knot Fruit is as shown in Figure 16.As can be seen that individually load the CH of Pd catalyst₄Catalytic oxidation stability is very poor, hence it is evident that is less than Pd@SiO₂Core-shell structure catalyst, confirm that nucleocapsid structure has excellent anti-sintering property from the negative.

Finally be necessary described herein be：Above example is served only for further detailed to technical scheme work Ground explanation, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the above of the invention Some the nonessential modifications and adaptations made belong to protection scope of the present invention.

Claims (10)

1. a kind of self-supporting metal or metal oxide core-shell structure catalyst, it is characterised in that：With below formula：xM- YMO@zShell/mAlO/ZT, wherein ZT represent the metal phase skeleton with porosity characteristic, and x represents that metal M is catalyzed in integrated Shared mass percent in agent, y represent metal oxide MO mass percents shared in integrated catalyst, and z is represented Mass percent shared in integrated catalyst Shell, m represent AlO quality percentages shared in integrated catalyst Number；And x is that 0~5%, y is that 0~10%, z is that 0.5~20%, m is 0.1~20%, surplus is metal phase (or nonmetallic phase) Mass percent shared by skeleton ZT.

2. self-supporting metal as claimed in claim 1 or metal oxide core-shell structure catalyst, it is characterised in that：It is described M be selected from least one of transition metal such as gold, silver, platinum, ruthenium, palladium, rhodium, nickel, copper；Described MO is selected from alkaline-earth metal, lanthanum It is at least one of rare earth metal, boron, aluminium, gallium, titanium, zirconium, zinc, Mn oxide；The roasting production of described Shell and coupling agent Thing is relevant, is silicon, aluminium, rare earth, tin, phosphorus, boron, zirconium and at least one of titanyl compound and carbon material；The material of the ZT For any one in the metals such as nickel, copper, aluminium, stainless steel, ferrum-chromium-aluminum, copper-nickel alloy, brass.

3. self-supporting metal as claimed in claim 1 or metal oxide core-shell structure catalyst, it is characterised in that:X model Enclose for 0.2-4.0%；Y scope is 2-8%；Z scope is 1-10%, and surplus is the quality percentage shared by metal phase skeleton ZT Number.

4. self-supporting metal as claimed in claim 1 or metal oxide core-shell structure catalyst, it is characterised in that：It is described Metal core be preferably at least one of Pd, Pt, Au, Ag, Fe, Co, Ni；Metal oxide core be preferably cerium, lanthanum, gallium, titanium, At least one of zirconium, magnesium, calcium, manganese, potassium oxide；Described ZT metal phase carrier mediums preferably are selected from aluminium, copper, nickel, copper-nickel alloy, no One kind in rust steel, ferrum-chromium-aluminum.

5. self-supporting metal as claimed in claim 1 or metal oxide core-shell structure catalyst, it is characterised in that：It is described ZT is the combination of any one or more in foam metal, wire netting, wire, sheet metal, tubular metal；It is or described ZT is that a diameter of 4~150 microns of fiber or the monoblock type metal with three-dimensional porous structure formed by the fiber sintering are fine Dimension.

6. self-supporting metal or metal oxide core-shell structure catalyst as described in any one in claim 1-5, it is special Sign is：The porosity of the catalyst is 60~98%.

7. the preparation method of a kind of self-supporting metal or metal oxide core-shell structure catalyst, it is characterised in that including as follows Step：

A) first with acid or alkali to metal phase (or nonmetallic phase) skeleton ZT processing, then ZT is put into pure water or contains silicon source Hydro-thermal process and/or heat treatment are carried out at a certain temperature with the stainless steel water heating kettle of the alkali source aqueous solution, and it is right after room temperature to be down to Sample is cleaned and dried, and realizes boehmite AlOOH nanometer sheets or Al₂O₃Anchor of the nanometer sheet on ZT surfaces is grown nonparasitically upon another plant length, system Derived from supporting al O/ZT complex carriers；

B) organic solution containing at least one metal M ion being coordinated with coupling agent impregnates obtained AlO/ZT carriers, makes idol Join after the surface hydroxyl in agent and AlO/ZT carriers carries out spontaneous polycondensation, by drying, being calcined and/or reduce, be made described Self-supporting metal or metal oxide core-shell structure catalyst, are designated as：xM-yMO@zShell/mAlO/ZT.

8. preparation method as claimed in claim 7, it is characterised in that step (a) source of aluminium be sodium metaaluminate, aluminum nitrate, Aluminum sulfate and aluminium chloride；The alkali source is urea, sodium hydroxide, sodium carbonate and sodium acid carbonate.

9. preparation method as claimed in claim 7, it is characterised in that step (b) coupling agent is silane coupler, metatitanic acid Ester coupling agent, aluminate coupling agent, bimetallic coupling agent, phosphate coupling agent, zirconium ester coupling agent, stannic acid ester coupling agent, boron At least one of acid esters coupling agent and lignin coupling agent.

10. a kind of self-supporting metal or oxide core-shell structure catalyst are applied to low-concentration methane and volatile organic compound Thing (VOCs) catalytic oxidation, catalyzing carbon monoxide oxidation reaction, preparing low-carbon olefin (FTO), methane conversion system In the reaction of synthesis gas.