CN103100415A - Catalyst with active component nano particles embedded in molecular sieve to crystallize, method and application - Google Patents
Catalyst with active component nano particles embedded in molecular sieve to crystallize, method and application Download PDFInfo
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- CN103100415A CN103100415A CN2012105097292A CN201210509729A CN103100415A CN 103100415 A CN103100415 A CN 103100415A CN 2012105097292 A CN2012105097292 A CN 2012105097292A CN 201210509729 A CN201210509729 A CN 201210509729A CN 103100415 A CN103100415 A CN 103100415A
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Abstract
The invention discloses a catalyst with active component nano particles embedded in a molecular sieve to crystallize. The catalyst comprises metal active component nano particles and a molecular sieve, the catalyst comprises metal active component nano particles are embedded and dispersed in the molecular sieve, the content of the active component nano particles in the catalyst is 2-70wt%, the particle size of the active component nano particles is 4-200nm, the crystal grain size of the molecular sieve is 1-10mu m; and the invention further discloses a preparation method and an application of the catalyst. The active metal in the catalyst disclosed by the invention is embedded and dispersed in the molecular sieve, the particle size is small; the metal active centre is effectively matched with an acid centre, the heavy constituent product can be effectively cracked; the catalytic activity is high, the metal reducibility is high, and the methane selectivity is low; the Fischer-Tropsch reaction activity cannot be reduced; the preparation process is simple, the cost is recued, and the catalyst is suitable for large industrial application; and the molecular sieve cannot break due to the difference of thermal coefficients of expansion, and the mechanical strength is high.
Description
Technical field
The present invention relates to a kind of catalyst, preparation method and application thereof; Especially relate to catalyst, method and application that a kind of active component nano particle embeds crystallization of molecular sieves.
Background technology
Under the world petroleum resource background that deficient and energy crisis highlights day by day gradually, C-1 chemistry (C
1Chemistry) broad research and fast development have been obtained.As raw material, the process that synthetic preparation contains the carbon chain growth of two or more carbon atom organic compounds is called C-1 chemistry take compound (as CO, methane, methyl alcohol, hydrogen cyanide etc.) that a carbon atom is only arranged.The C-1 chemistry raw material sources are extensive; can reduce the undue dependence to petroleum resources; it is the most important and the most promising approach that the petroleum replacing synthetic route prepares basic organic chemical industry raw material, fuel and other important chemical; comprise that Fischer-Tropsch is synthetic; the synthesis gas through methanol one-step method prepares dimethyl ether, low-carbon alkene, aromatic hydrocarbons; methane aromatic hydrocarbons processed, the important course of reaction such as hydroformylation reaction.
Nineteen twenty-three, Germany scientist Frans Fischer and Hans Tropsch have invented Fischer-Tropsch synthesis method (Fischer-Tropsch Synthesis, abbreviation F-T is synthetic or Fischer-Tropsch is synthetic).Fischer-Tropsch is synthetic is the non-petroleum base fossil fuels such as coal, natural gas, living beings to be converted into the important channel of liquid fuel and the high valuable chemicals of cleaning, high-quality.Fischer-Tropsch product has without sulphur, without many merits such as nitrogen, aromatic-frees than traditional petroleum derivative, can satisfy day by day harsh environmental requirement.Along with petroleum resources exhaust gradually and world wide in constantly soaring to new forms of energy and resource requirement, the approach by Fischer-Tropsch synthesis prepare liquid fuel or high valuable chemicals has obtained extensive approval.
Fischer-Tropsch is synthetic is a very complicated reaction system, although course of reaction is with simple synthesis gas (CO and H
2) be raw material, but the product after synthetic is obeyed the Anderson-Schulz-Flory regularity of distribution, namely only has methane and macromolecule wax to have higher selective, all the other cuts are selective restriction all.Reduce methane and generate, optionally synthetic target hydro carbons (liquid fuel, heavy hydrocarbon or alkene etc.) and the catalyst of researching and developing controlled selectivity of product are the synthetic research direction of Fischer-Tropsch all the time.Molecular sieve is widely applied in Fischer-Tropsch is synthetic due to pore passage structure and the excellent acid catalysis function of its high-sequential.
In Fischer-Tropsch is synthetic, molecular sieve can with the effective combination of Fischer-Tropsch synthesizing activity component, to reach the purpose of regulation and control Fischer-Tropsch synthetic.Wherein, the most frequently used is conventional impregnation, namely take molecular sieve as carrier, dipping fischer-tropsch activity metal (Fe, Co, Ru etc.) and auxiliary agent (as Mn, Cu, Zr, Mg, Zn, Ce, K etc.), can be carried out cracking and isomerization reaction and be decomposed into light hydrocarbon on molecular sieve by the long chain hydrocarbon of the synthetic preparation of Fischer-Tropsch, the regulation and control Fischer-Tropsch synthetic distributes.But this type of loaded catalyst has following defective: 1) most of reactive metal is positioned at molecular sieve outer surface; 2) particle size is large; 3) metal active center and acid site can not effectively be mated, the effectively cracking of heavy constituent product; 4) due to interaction strong between metal and molecular sieve, cause that catalytic activity is low, the metallic reducing degree is poor, methane selectively is high.What another research was more is the physical mixed method, be about to fischer-tropsch synthetic catalyst and molecular sieve and carry out mechanical mixture, make the physics mixed catalyst, synthesis gas can carry out cracking and isomerization reaction on molecular sieve in its vicinity in the Fischer-Tropsch product of reactive metal, and wherein the cracking of waxy product can effectively suppress the inactivation of catalyst.But the cracking of carrying out on the physical mixed catalyst and isomerization reaction are random, the direct desorption of hydrocarbon partial and can not effectively contacting with the acidic zeolite position, and the acid catalysis function of molecular sieve fails to be utilized effectively.
It is synthetic that Japan Noritatsu Tsubaki seminar is used for Fischer-Tropsch with the molecular screen membrane coated catalyst, at conventional load type fischer-tropsch catalysts (as Co/SiO
2, Co/Al
2O
3) etc. surface construction molecular screen membrane (as HZSM-5, H-β), with coupling (Angew.Chem., 2008,120:359-362, the Energy﹠amp that realizes Fischer-Tropsch catalytic process and the separation process of film base; Fuels, 2008,22,1463-1468).In this type of molecular screen membrane coated catalyst, synthesis gas is by molecular screen membrane and fischer-tropsch catalysts reaction, the long chain hydrocarbon that wherein generates enters molecular screen membrane and carries out cracking and isomerization reaction, and the confinement effect of molecular sieve pore passage can suppress the absorption again of desorption product.In addition, because cracking reaction is the endothermic reaction, can absorb the fischer-tropsch reaction liberated heat, avoid beds overheated, slow down catalyst deactivation rate.But this type of molecular sieve film catalyst has following defective: 1) generally all directly construct on millimetre-sized catalyst nucleus surface, the existence of molecular screen membrane can increase CO and H
2Diffusional resistance, reduce fischer-tropsch reaction active; 2) preparation process of molecular screen membrane is complicated, often needs various preprocessing process, and the generation of molecular screen membrane requires catalyst and molecular screen membrane that compatibility is preferably arranged, and film-forming quality is wayward, tends to form the defectives such as crack, pin hole; 3) molecular screen membrane is removed by roasting in the process of template, and molecular screen membrane may be because break because of the difference of coefficient of thermal expansion with fischer-tropsch catalysts, and the erosion of strong basicity molecular screen membrane precursor synthesis liquid also can cause the mechanical strength of catalyst to descend.Therefore, design can be with the new structure catalyst of acidic zeolite center and Fischer-Tropsch metal active center efficient coupling, for the acid catalysis function of giving full play to molecular sieve, improve Fischer-Tropsch synthetic in target product selectively significant.
The synthesis gas through methanol one-step method prepares the processes such as dimethyl ether, low-carbon alkene, aromatic hydrocarbons and refers to that synthesis gas first catalyzes and synthesizes methyl alcohol, methyl alcohol generates the course of reaction of dimethyl ether, low-carbon alkene, aromatic hydrocarbons etc. again on the catalyst such as molecular sieve, along with the rise of oil price and reaching its maturity of methanol production technology, the exploitation Downstream Products of Methanol has great industrial prospect and realistic meaning.In traditional two-step method process, synthetic route is long, and equipment investment is large, and one-step method can be saved pilot process with synthesizing methanol and two PROCESS COUPLING of molecular sieve catalytic, reduces equipment investment and operating cost, increases economic efficiency, and directly obtains required target product.
In addition, for the production of dimethyl ether, industrial main employing methanol gas phase dehydration, be traditional two-step method, synthesis gas is the standby methyl alcohol of Hydrogenation on copper-based catalysts first, and methyl alcohol is dehydration generation dimethyl ether on solid acid catalyst again, this synthetic route is long, and equipment investment is large.The one-step method from syngas preparing dimethy ether refers to above-mentioned two-step reaction is concentrated in a reactor and carries out, but the methyl alcohol Direct Dehydration of generation obtains dimethyl ether.At present, to prepare dimethyl ether be mainly with catalyst for methanol and solid acid catalyst physical mixed to one-step method from syngas.
Methane molecular weight in hydrocarbon compound is minimum and the most stable, and the bond energy of its hydrocarbon key is very high, and respond is low, is difficult for liquefaction, and the hydrocarbon phase ratio higher with other molecular weight is difficult to directly utilize as industrial chemicals, and the trans-utilization of methane is significant.Methane aromatizing is to be accompanied by the direct important channel that fully utilizes of methane that methane oxidation coupling grows up, comprise methane oxidation aromatisation and anaerobic aromatization both direction, not methane oxidation aromatisation selectively often not high, benzene selectively very low, and in the oxygen-free aromatization reaction of methane process owing to not using oxygen, avoided burning and the deep oxidation of methane, and its product aromatic hydrocarbons being easy to other product separation, is a promising direction of methyl hydride catalyzed conversion.It is catalyst based that the methane non oxidative aromatization used catalyst is mainly molecular sieve carried Mo, as Mo/HZSM-5 etc.
Hydroformylation reaction is alkene and synthesis gas (CO and H
2) react generation than the course of reaction of the aldehyde of former alkene bull point or alcohol under the transition metal complex catalysts effect.The traditional industry used catalyst is rhodium-and-phosphine composition, as [Rh (CO) (TPPTS)
3] [TPPTS=P (m-C
6H
4SO
3Na)
3] etc., this type of catalyst is difficult to separate from liquid phase and reclaim.For addressing this problem, development in recent years the active component solid-supported catalyst, but that this type of catalyst is difficult to obtain high n-alkanal is selective, and n-alkanal has higher industrial application value.
Summary of the invention
First technical problem that the present invention will solve is to provide the catalyst that a kind of active component nano particle embeds crystallization of molecular sieves.This catalyst activity metallic particles embeds and is distributed in molecular sieve; Particle size is little, reaches nanoscale; Metal active center and acid site can effectively be mated, the effectively cracking of heavy constituent product; Catalytic activity is high, the metallic reducing degree is high, methane selectively is low; Do not reduce the fischer-tropsch reaction activity; Preparation process is simple, cost, and suitability for mass industrialized is used; Molecular sieve can not break because of the difference of coefficient of thermal expansion, and mechanical strength is high.
Second technical problem that the present invention will solve is to provide the preparation method that a kind of active component nano particle embeds the catalyst of crystallization of molecular sieves.
The 3rd technical problem that the present invention will solve is to provide the application that a kind of active component nano particle embeds the catalyst of crystallization of molecular sieves.
For solving above-mentioned first technical problem, the present invention adopts following technological means:
A kind of active component nano particle embeds the catalyst of crystallization of molecular sieves, comprise metal active constituent nano particle and molecular sieve, described metal active constituent nano particle embeds and is dispersed in molecular sieve, described metal active constituent nano particle content in catalyst is 2～70wt%, the reactive metal nano particle diameter is 4～200nm, and the zeolite crystal size is 1～10 μ m.
Preferably, the reactive metal nano particle diameter is 4～100nm; More preferably, the reactive metal nano particle diameter is 4～50nm; Most preferably, the reactive metal nano particle diameter is 5～30nm;
Preferably, described metal active constituent nano particle content in catalyst is 9～60wt%; More preferably, described metal active constituent nano particle content in catalyst is 9～40wt%; Most preferably, described metal active constituent nano particle content in catalyst is 17～21wt%.
Preferably, described metal active constituent nano particle is one or more in following active component nano particle: Fe, Co, Ru, Cu, Pd, Ni, Rh, Pt, Mo.
Preferably, described molecular sieve be in following molecular sieve one or more: HZSM-5 molecular sieve, H beta-molecular sieve, Silicate-1 molecular sieve, MCM-41 molecular sieve, HMS molecular sieve, SBA-15 molecular sieve, HY molecular sieve, SAPO-34 molecular sieve, TS-1 molecular sieve.
Preferably, also comprise auxiliary agent in catalyst.More preferably, described auxiliary agent is one or more in oxide, reduction-state particle or the metal alloy of following element: Mn, Cu, Zr, Mg, Cr, Zn, Ce, K, Al, Ag, Pd, Pt, Ru, Rh.
For solving above-mentioned second technical problem, a kind of active component nano particle of the present invention embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
1) get the support type that contains silicon, aluminium, titanium or phosphorus or co-precipitated catalyst as the presoma catalyst, the presoma catalyst is pulverized, mistake 〉=20 mesh sieves get the presoma catalyst fines; Contain the metal active constituent nano particle in described presoma;
2) get silicon source, aluminium source, titanium source or phosphorus source, the mixed solution of water and ethanol dissolves, then adds template and presoma catalyst fines, stirs, and gets synthetic liquid; Those skilled in the art understand, and when getting silicon source, aluminium source, titanium source or phosphorus source, be complementary with the presoma catalyst; As a rule the element of presoma catalyst and the silicon source of getting later, aluminium source, titanium source or phosphorus source will be mated, and namely not identical, for example siliceous in the presoma catalyst, the back is not selected the silicon source in order to avoid repeats;
3) the pH value greater than 8 condition under, step 2) the synthetic liquid that obtains carries out hydrothermal synthesis reaction in the reactor of sealing; Filter after reaction and to get catalyst in the middle of solid, with catalyst in the middle of deionized water or ethanol washing solid to washing lotion pH value less than 8; Described hydrothermal synthesis reaction refers to that temperature is that 100～1000 ℃, pressure are to utilize synthetic that in the aqueous solution, the material chemical reaction carries out under 1MPa～1GPa condition;
4) catalyst in the middle of solid is dry under 80～150 ℃, join 350～600 ℃ of roastings, with removed template method, obtain product.
Preferably, in step 1), described metal active constituent nano particle is one or more in following active component nano particle: Fe, Co, Ru, Cu, Pd, Ni, Rh, Pt, Mo.
Preferably, in step 1), the carrier of described presoma catalyst is to contain one or more oxide carrier of Si, Al, Ti, P; The presoma catalyst comprises metal active constituent nano particle and carrier;
Preferably, also contain builder granule in described presoma catalyst, the content of auxiliary agent in the presoma catalyst is 2～50wt%; Preferably, the content of auxiliary agent in the presoma catalyst is 2～20wt%; Preferably, the content of auxiliary agent in the presoma catalyst is 4～14wt%; More preferably, described auxiliary agent is one or more in oxide, reduction-state particle or the metal alloy of following element: Mn, Cu, Zr, Mg, Cr, Zn, Ce, K, Al, Ag, Pd, Pt, Ru, Rh.
Preferably, step 2) in, described silicon source is selected from one or more in following material: ethyl orthosilicate (TEOS), Ludox (Silica Gel), methyl silicate (TMeOS), sodium metasilicate (Na
2SiO
3); Described aluminium source is selected from one or more in following material: aluminum nitrate (Al (NO
3)
3), aluminum sulfate (Al
2(SO
4)
3), aluminium chloride (AlCl
3), aluminium isopropoxide ([(CH
3)
2CHO]
3Al); Described titanium source is selected from one or more in following material: butyl titanate (Ti (OC
4H
9)
4), titanium tetrachloride (TiCl
4), titanyl sulfate (TiOSO
4); Described phosphorus source is selected from one or more in following material: tributyl phosphate (OP (OCH
2CH
2CH
2CH
3)
3), phosphoric acid (H
3PO
4), metaphosphoric acid (HPO
3).
Preferably, step 2) in, described template be TPAOH (be called for short: TPAOH), tetraethyl ammonium hydroxide (be called for short: TEAOH), TMAH (be called for short: TMAOH), softex kw (be called for short: CTAB), PEO-PPOX-PEO triblock copolymer (be called for short: P123) or octadecylamine (be called for short: ODA).
Preferably, step 2) in, in described synthetic liquid, the mol ratio of each component is: silicon, aluminium, titanium and/or phosphorus: template: ethanol: water=5～100:8～90:50～1000:100～3000.Preferably, described silicon, aluminium, titanium and/or phosphorus: template: ethanol: water=40～60:10～20:400～600:500～1000.
Preferably, being incorporated as dropwise of template adds.
Preferably, in step 3), reaction temperature is 140～260 ℃, and the reaction time is 20～750 hours, and reaction pressure is 1～30MPa.
Preferably, in step 3), described reactor is with teflon-lined stainless steel water thermal synthesis still.
Preferably, in step 4), be 2～12 hours drying time; Roasting time is 2～12 hours.
For solving above-mentioned the 3rd technical problem, a kind of active component nano particle embeds the catalyst of crystallization of molecular sieves and uses in the correlated response process of C-1 chemistry.
Preferably, described C-1 chemistry correlated response process comprises that Fischer-Tropsch is synthetic, and the synthesis gas through methanol one-step method prepares dimethyl ether, low-carbon alkene, aromatic hydrocarbons, methane aromatic hydrocarbons processed or hydroformylation reaction.
Preferably, in described C-1 chemistry correlated response process, adopt fixed bed reactors, fluidized-bed reactor or paste state bed reactor.
The present invention has following beneficial effect:
1) new structure catalyst of the present invention comprises active component nano particle and molecular sieve two parts, building-up process is simple, the preparation of employing hydrothermal synthesis method, building-up process is with traditional siliceous, aluminium, titanium, the support type of phosphorus or co-precipitated catalyst are presoma, the silicon of its stripping, aluminium, titanium, phosphorus is as the silicon source of synthesis of molecular sieve, the aluminium source, the titanium source, all or part of of phosphorus source, crystallization velocity by controlling dissolution rate in building-up process and molecular sieve is (as changing presoma catalyst fines granularity, regulate synthetic liquid pH value, adjust hydrothermal temperature, pressure and time etc.), the active component nano particle can be embedded crystallization of molecular sieves, structural behaviour is excellent,
2) new structure catalyst of the present invention can be with the acid catalysis function efficient coupling of acid catalysis function and the active component of molecular sieve, the product that generates on active component can be by the acid catalysis character of molecular sieve excellence and the further reaction and separation processes of pore passage structure of high-sequential, this synergy can be with the multistep reaction PROCESS COUPLING, one-step synthesis meets the target product of purity and yield requirement, the Effective Regulation product distributes, prevent that the catalyst activity component runs off, and slows down catalyst deactivation rate;
3) new structure catalyst of the present invention, catalyst life is long, and mechanical stability is good, can obtain important application in the C-1 chemistry correlated process.
Description of drawings
Fig. 1 is catalyst structure schematic diagram of the present invention;
Fig. 2 is transmission electron microscope (TEM) figure of the new structure catalyst that makes of embodiment 1;
Fig. 3 is catalyst cross section structure schematic diagram of the present invention.
The specific embodiment
Embodiment 1
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
1) Co/SiO
2The existing equi-volume impregnating preparation of presoma catalyst:
With SiO
2Process 2h for 200 ℃ in air, then with Co (NO
3)
26H
2O be the Co source to its incipient impregnation, reactive metal Co load capacity 20wt%, application of vacuum 1h, 120 ℃ of dry 12h, 400 ℃ of roasting 2h get the granular precursor catalyst; Be 80 purpose powder with the screening of granular precursor catalyst breakage;
2) take TPAOH as template, with Al (NO
3)
39H
2O is the Al source, with Co/SiO
2The Si of stripping is as the Si source in building-up process;
With Al (NO
3)
39H
2O with deionized water and ethanol (be called for short: Et OH) dissolving, after stirring, the presoma catalyst fines that adds step 1) to obtain dropwise adds template TPAOH, mixes, and gets synthetic liquid; In synthetic liquid, mol ratio is 1.0Al:50S i:15TPAOH:500Et OH:880H
2O；
3) will synthesize liquid sealing and carry out hydrothermal synthesis reaction in the stainless steel water thermal synthesis still with the polytetrafluoroethylene (PTFE) inner core, the Hydrothermal Synthesis temperature is 180 ℃, and generated time is 100h; Reaction is filtered catalyst after finishing from solution, get the middle catalyst of solid, washs to washing lotion pH value less than 8 with deionized water or ethanol;
4) with catalyst dry 12h under 120 ℃ in the middle of solid, be heated to 500 ℃ of roasting 5h, with removed template method, make new structure CoHZSM-5 molecular sieve catalyst.
After testing, the structure of CoHZSM-5 catalyst is shown in Figure 1, detects referring to Fig. 2 through transmission electron microscope (TEM).The CoHZSM-5 catalyst comprises Co active component nano particle and HZSM-5 molecular sieve, described Co active component nano particle embeds and is dispersed in the HZSM-5 molecular sieve, described Co active component nano particle content in catalyst is 19.8wt%, the reactive metal nano particle diameter is 10nm, and the zeolite crystal size is 5 μ m;
Above-mentioned gained CoHZSM-5 molecular sieve catalyst in the 10MPa lower sheeting, is got 20～40 purpose particles and is used for the performance test of fixed bed Fischer-Tropsch synthesis after pulverizing.The activation condition of catalyst is: under normal pressure with the H of 80ml/min
2At 400 ℃ of reduction 10h.The reaction condition of catalyst is: 260 ℃, and 1.0MPa, H
2/ CO mol ratio is 2.0, W
cat/ F=5gh mol
-1, reaction result is as shown in the table.
αI so-C
5-C
12Be C
5-C
12Middle branched paraffin selective.According to upper table as can be known, the catalyst that makes of embodiment 1 is to C
5-C
12Have good selective.
Embodiment 2
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
1) Co/Al
2O
3The existing equi-volume impregnating preparation of presoma catalyst
With carrier γ-Al
2O
3Process 2h for 200 ℃ in air, then with Co (NO
3)
26H
2O be the Co source to its incipient impregnation, reactive metal Co load capacity 20wt%, application of vacuum 1h, 120 ℃ of dry 12h, 400 ℃ of roasting 2h obtain the presoma catalyst; Be 20 purpose powder with the screening of gained presoma catalyst breakage;
2) take TPAOH as template, take TEOS as the Si source, with Co/Al
2O
3The Al of stripping is as the Al source in building-up process;
TEOS is mixed with deionized water and ethanol, and after stirring, the presoma catalyst fines that adds step 1) to obtain dropwise adds template afterwards, mixes, and gets synthetic liquid; In synthetic liquid, mol ratio is 1.0Al:50Si:15TPAOH:500EtOH:880H
2O；
3) will synthesize liquid sealing and carry out hydrothermal synthesis reaction in the stainless steel water thermal synthesis still with the polytetrafluoroethylene (PTFE) inner core, the Hydrothermal Synthesis temperature is 240 ℃, and generated time is 20h; Reaction is filtered catalyst after finishing from solution, get the middle catalyst of solid, washs to washing lotion pH value less than 8 with deionized water, ethanol;
4) with catalyst dry 10h under 120 ℃ in the middle of solid, be heated to 500 ℃ of roasting 10h, with removed template method, make new structure CoHZSM-5 molecular sieve catalyst.
The CoHZSM-5 catalyst comprises Co active component nano particle and HZSM-5 molecular sieve, described Co active component nano particle embeds and is dispersed in the HZSM-5 molecular sieve, described Co active component nano particle content in catalyst is 19.2wt% after testing, the reactive metal nano particle diameter is 12nm, and the zeolite crystal size is 5 μ m;
Gained CoHZSM-5 molecular sieve catalyst in the 10MPa lower sheeting, is got 20-40 purpose particle and is used for the performance test of fixed bed Fischer-Tropsch synthesis after pulverizing.
The fischer-tropsch reaction activity rating of catalyst is with embodiment 1, and reaction result is as shown in the table.
αIso-C
5-C
12Be C
5-C
12Middle branched paraffin selective.
Embodiment 3
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
Adopt traditional equi-volume impregnating to prepare Co-Zr/SiO
2Catalyst:
With SiO
2Process 2h for 200 ℃ in air, then with Co (NO
3)
26H
2O and Zr (NO
3)
45H
2The aqueous solution of O is to its incipient impregnation, and reactive metal Co load capacity is 20wt%, and auxiliary agent Zr load capacity is 6wt%, application of vacuum 1h, and 120 ℃ of dry 12h, 400 ℃ of roasting 2h obtain Co-Zr/SiO
2The presoma catalyst; Be 60 purpose powder with the screening of gained presoma catalyst breakage;
All the other operating procedures prepare new structure Co-ZrHZSM-5 molecular sieve catalyst with embodiment 1.The Co-ZrHZSM-5 catalyst comprises Co active component nano particle, Zr builder granule and HZSM-5 molecular sieve, described Co active component nano particle embeds and is dispersed in the HZSM-5 molecular sieve, described Co active component nano particle content in catalyst is 19.0wt% after testing, the reactive metal nano particle diameter is 9nm, and the zeolite crystal size is 5 μ m;
Gained Co-ZrHZSM-5 molecular sieve catalyst in the 10MPa lower sheeting, is got 20～40 purpose particles and is used for the Fischer-Tropsch synthesis performance test after pulverizing.The fischer-tropsch reaction activity rating of catalyst is with embodiment 1, and reaction result is as shown in the table.
αIso-C
5-C
12Be C
5-C
12Middle branched paraffin selective.
Embodiment 4
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
Adopt traditional equi-volume impregnating to prepare Co-Ru/Al
2O
3The presoma catalyst; Carrier γ-Al
2O
3Process 2h for 200 ℃ in air, afterwards with Co (NO
3)
26H
2O and RuCl
3The aqueous solution to its incipient impregnation, reactive metal Co load capacity is 20wt%, auxiliary agent Ru load capacity is 2wt%, application of vacuum 1h, 120 ℃ of dry 12h, 400 ℃ of roasting 2h obtain the presoma catalyst; Be 80 purpose powder with the screening of gained presoma catalyst breakage;
All the other operating procedures prepare new structure Co-RuHZSM-5 molecular sieve catalyst with embodiment 2.The Co-RuHZSM-5 catalyst comprises Co active component nano particle, Ru builder granule and HZSM-5 molecular sieve, described Co active component nano particle embeds and is dispersed in the HZSM-5 molecular sieve, described Co active component nano particle content in catalyst is 19.4wt% after testing, the reactive metal nano particle diameter is 8nm, and the zeolite crystal size is 5 μ m;
Gained Co-RuHZSM-5 molecular sieve catalyst in the 10MPa lower sheeting, is got 20～40 purpose particles and is used for the Fischer-Tropsch synthesis performance test after pulverizing.The fischer-tropsch reaction activity rating of catalyst is with embodiment 1, and reaction result is as shown in the table.
αIso-C
5-C
12Be C
5-C
12Middle branched paraffin selective.
Embodiment 5
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
Adopt traditional excessive infusion process to prepare Fe-Mn-K/SiO
2The presoma catalyst is with SiO
2Process 2h for 200 ℃ in air, afterwards it is added a certain amount of Fe (NO
3)
39H
2O, Mn (NO
3)
24H
2O, KNO
3Mixed solution in (reactive metal Fe load capacity 20wt%, the load capacity of auxiliary agent Mn, K is respectively 6wt%, 4wt%), 70 ℃ are continuously stirring to the most of evaporation of water, put into afterwards 120 ℃ of dry 12h of drying box, 400 ℃ of roasting 2h obtain the presoma catalyst; Be 120 purpose powder with the screening of gained presoma catalyst breakage;
All the other operating procedures prepare new structure Fe-Mn-KHZSM-5 molecular sieve catalyst with embodiment 1.
The Fe-Mn-KHZSM-5 catalyst comprises Fe active component nano particle, Mn and K builder granule and HZSM-5 molecular sieve, described Fe active component nano particle embeds and is dispersed in the HZSM-5 molecular sieve, described Fe active component nano particle content in catalyst is 18.8wt% after testing, the active Fe nano particle diameter is 12nm, and the zeolite crystal size is 5 μ m;
Gained Fe-Mn-KHZSM-5 molecular sieve catalyst in the 10MPa lower sheeting, is got 20～40 purpose particles and is used for the Fischer-Tropsch synthesis performance test after pulverizing; The activation condition of catalyst is: under normal pressure with the synthesis gas (H of 38ml/mi n
2/ CO mol ratio is 1.0) at 300 ℃ of reduction 10h.The reaction condition of catalyst is: 280 ℃, and 1.0MPa, H
2/ CO mol ratio is 1.0, W
cat/ F=5ghmol
-1, reaction result is as shown in the table.
αC
2 =-C
4 =Be C
2-C
4Middle alkene selective
Embodiment 6
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
Adopt traditional coprecipitation to prepare Co-Zr-Al presoma catalyst; Proportionally prepare Co (NO
3)
26H
2O, Zr (NO
3)
45H
2O and Al (NO
3)
39H
2The mixed solution of O (Co, Zr, Al in solution
2O
3Mass ratio be 20:6:100), with (NH
4)
2CO
3Be precipitating reagent, continuous uniform co-precipitation in the water bath with thermostatic control of 60 ℃, vigorous stirring, regulate simultaneously charging rate take the pH value of controlling precipitated liquid as 7 ± 0.2, after the precipitation end, continue to stir 1h, still aging spending the night filtered afterwards and washed to washing lotion pH value less than 8 with deionized water and ethanol, afterwards 120 ℃ of dry 12h, 400 ℃ of roasting 2h obtain the presoma catalyst; Be 180 purpose powder with the screening of gained presoma catalyst breakage;
All the other operating procedures prepare new structure Co-ZrHZSM-5 molecular sieve catalyst with embodiment 2.
The Co-ZrHZSM-5 catalyst comprises Co active component nano particle, Zr builder granule and HZSM-5 molecular sieve, described Co active component nano particle embeds and is dispersed in the HZSM-5 molecular sieve, described Co active component nano particle content in catalyst is 19.7wt% after testing, active Co nano particle diameter is 15nm, and the zeolite crystal size is 5 μ m;
Gained Co-ZrHZSM-5 molecular sieve catalyst in the 10MPa lower sheeting, is got 20～40 purpose particles and is used for the Fischer-Tropsch synthesis performance test after pulverizing.The fischer-tropsch reaction activity rating of catalyst is with embodiment 1, and reaction result is as shown in the table.
αIso-C
5-C
12Be C
5-C
12Middle branched paraffin selective.
Embodiment 7
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
Adopt traditional coprecipitation to prepare Fe-Mn-Cu-K-Al presoma catalyst.Proportionally prepare Fe (NO
3)
39H
2O, Mn (NO
3)
24H
2O, Cu (NO
3)
23H
2O, KNO
3And Al (NO
3)
39H
2The mixed solution of O (Fe, Mn, Cu, K, Al in catalyst
2O
3Mass ratio be 20:6:6:2:100), with K
2CO
3Be precipitating reagent, continuous uniform co-precipitation in the water bath with thermostatic control of 60 ℃, vigorous stirring, regulate simultaneously charging rate take the pH value of controlling precipitated liquid as 7 ± 0.2, after precipitation finishes, continue stirring 1h, still aging spending the night, filter afterwards and wash to washing lotion pH value less than 8 with deionized water and ethanol, 120 ℃ of dry 12h afterwards, 400 ℃ of roasting 2h; Be 80 purpose powder with gained beaded catalyst crushing and screening;
All the other operating procedures prepare new structure Fe-Mn-Cu-KHZSM-5 molecular sieve catalyst with embodiment 2.The Fe-Mn-Cu-KHZSM-5 catalyst comprises Fe active component nano particle, auxiliary agent Mn and auxiliary agent Cu and auxiliary agent K particle and HZSM-5 molecular sieve, described Fe active component nano particle embeds and is dispersed in the HZSM-5 molecular sieve, described Fe active component nano particle content in catalyst is 17.9wt%, the active Fe nano particle diameter is 19nm, and the zeolite crystal size is 5 μ m;
Gained Fe-Mn-Cu-KHZSM-5 molecular sieve catalyst in the 10MPa lower sheeting, is got 20-40 purpose particle and is used for the Fischer-Tropsch synthesis performance test after pulverizing.The fischer-tropsch reaction activity rating of catalyst is with embodiment 5, and reaction result is as shown in the table.
αC
2 =-C
4 =Be C
2-C
4Middle alkene selective.
Embodiment 8:
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
Co/SiO
2The preparation of presoma catalyst adopts hydrothermal synthesis method to prepare the CoH beta catalyst, take tetraethyl ammonium hydroxide (TEAOH) as template, with Al (NO with embodiment 1
3)
39H
2O is the Al source, with Co/SiO
2The Si of stripping is as the Si source in building-up process; Synthetic liquid mol ratio is 1.0Al:70Si:80TEAOH:900EtOH:2000H
2O；
With Al (NO
3)
39H
2O is with deionized water and ethanol dissolving, after stirring, add the catalyst precursor powder, dropwise add afterwards template TEAOH, mix, to synthesize afterwards liquid sealing in the stainless steel water thermal synthesis still with the polytetrafluoroethylene (PTFE) inner core, the Hydrothermal Synthesis temperature is 155 ℃, and generated time is 80h.After reaction finishes, catalyst is filtered from solution, wash to washing lotion pH value less than 8 with deionized water, ethanol, 120 ℃ of dry 12h afterwards, 500 ℃ of roasting 5h removed template methods namely prepare new structure CoH beta-molecular sieve catalyst.
The CoH beta catalyst comprises Co active component nano particle and H beta-molecular sieve, described Co active component nano particle embeds and is dispersed in the H beta-molecular sieve, described Co active component nano particle content in catalyst is 19.5wt% after testing, active Co nano particle diameter is 12nm, and the zeolite crystal size is 2 μ m;
Gained CoH beta-molecular sieve catalyst in the 10MPa lower sheeting, is got 20～40 purpose particles and is used for the performance test of fixed bed Fischer-Tropsch synthesis after pulverizing.The fischer-tropsch reaction activity rating of catalyst is with embodiment 1, and reaction result is as shown in the table.
αIso-C
5-C
12Be C
5-C
12Middle branched paraffin selective.
Embodiment 9:
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
Co/Al
2O
3The preparation of presoma catalyst adopts hydrothermal synthesis method to prepare the CoH beta catalyst, take tetraethyl ammonium hydroxide (TEAOH) as template, with Al (NO with embodiment 2
3)
39H
2O is the Al source, with Co/SiO
2The Si of stripping is as the Si source in building-up process; The synthetic solvent mol ratio is 2.0Al:50Si:50TEAOH:500EtOH:880H
2O；
TEOS is mixed with deionized water and ethanol, after stirring, add the catalyst precursor powder, dropwise add afterwards template, mix, to synthesize afterwards liquid sealing in the stainless steel water thermal synthesis still with the polytetrafluoroethylene (PTFE) inner core, the Hydrothermal Synthesis temperature is 155 ℃, and generated time is 500h; After reaction finishes, catalyst is filtered from solution, wash to washing lotion pH value less than 8 with deionized water, ethanol, 120 ℃ of dry 2h afterwards, 500 ℃ of roasting 5h removed template methods namely prepare new structure CoH
The beta-molecular sieve catalyst.
The CoH beta catalyst comprises Co active component nano particle and H beta-molecular sieve, described Co active component nano particle embeds and is dispersed in the H beta-molecular sieve, described Co active component nano particle content in catalyst is 19.5wt%, active Co nano particle diameter is 14nm, and the zeolite crystal size is 2 μ m;
Gained CoH beta-molecular sieve catalyst in the 10MPa lower sheeting, is got 20～40 purpose particles and is used for the performance test of fixed bed Fischer-Tropsch synthesis after pulverizing.The fischer-tropsch reaction activity rating of catalyst is with embodiment 1, and reaction result is as shown in the table.
αIso-C
5-C
12Be C
5-C
12Middle branched paraffin selective.
Embodiment 10:
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
1) preparation of Cu-Zn-Al presoma catalyst
Adopt traditional coprecipitation to prepare Cu-Zn-Al presoma catalyst: to prepare according to a certain percentage Cu (NO
3)
23H
2O, Zn (NO
3)
26H
2O and Al (NO
3)
39H
2The mixed solution of O (in catalyst, the mol ratio of Cu, Zn, Al is 6:3:1) is with (NH
4)
2CO
3Be precipitating reagent, continuous uniform co-precipitation in the water bath with thermostatic control of 60 ℃, vigorous stirring, regulate simultaneously charging rate take the pH value of controlling precipitated liquid as 7 ± 0.2, after precipitation finishes, continue stirring 1h, still aging spending the night, filter afterwards and wash to washing lotion pH value less than 8 with deionized water and ethanol, 120 ℃ of dry 5h afterwards, 350 ℃ of roasting 3h.Be 80 purpose powder with gained beaded catalyst crushing and screening;
2) preparation of new structure Cu-ZnH beta catalyst
Adopt hydrothermal synthesis method to prepare the Cu-ZnH beta catalyst, take tetraethyl ammonium hydroxide (TEAOH) as template, with Al (NO
3)
39H
2O is the Al source, with Co/SiO
2The Si of stripping is as the Si source in building-up process.The synthetic solvent mol ratio is 10Al:20Si:15TEAOH:300EtOH:500H
2O；
With Al (NO
3)
39H
2O is with deionized water and ethanol dissolving, after stirring, add the catalyst fines in step 1), dropwise add afterwards template TEAOH, mix, to synthesize afterwards liquid sealing in the stainless steel water thermal synthesis still with the polytetrafluoroethylene (PTFE) inner core, the Hydrothermal Synthesis temperature is 155 ℃, and generated time is 80h.After reaction finishes, catalyst is filtered from solution, wash to washing lotion pH value less than 8 with deionized water, ethanol, 140 ℃ of dry 12h afterwards, 600 ℃ of roasting 2h removed template methods; Obtain new structure Cu-ZnH beta-molecular sieve catalyst.
The Cu-ZnH beta catalyst comprises Cu active component nano particle, auxiliary agent Zn particle and H beta-molecular sieve, described Cu active component nano particle embeds and is dispersed in the H beta-molecular sieve, described Cu active component nano particle content in catalyst is 60.4wt%, active Cu nano particle diameter is 20nm, and the zeolite crystal size is 2 μ m;
Gained Cu-ZnH beta catalyst in the 10MPa lower sheeting, is got 20～40 purpose particles for the synthesis of the performance test of gas one-step method reaction of preparing dimethyl ether after pulverizing; The activation condition of catalyst is: under normal pressure with the H of 60ml/min
2At 220 ℃ of reduction 10h.The reaction condition of catalyst is: 250 ℃, and 3.0MPa, H
2/ CO mol ratio is 1.5, W
cat/ F=5ghmol
-1, reaction result is as shown in the table:
Production has good selective the present embodiment catalyst to dimethyl ether.
Embodiment 11:
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, comprises the steps:
1) Pd/Al
2O
3The preparation of presoma catalyst
Adopt traditional equi-volume impregnating, with carrier γ-Al
2O
3Process 2h for 200 ℃ in air, afterwards with Pd (NO
3)
22H
2O be the Pd source to its incipient impregnation, reactive metal Pd load capacity 10wt%, application of vacuum 1h, 120 ℃ of dry 12h, 400 ℃ of roasting 2h are with gained Pd/Al
2O
3The screening of presoma catalyst breakage is 70 purpose powder;
2) preparation of new structure PdHZSM-5 catalyst
Adopt hydrothermal synthesis method to prepare the PdHZSM-5 catalyst: take TPAOH (TPAOH) as template, take ethyl orthosilicate (TEOS) as the Si source, with Co/Al
2O
3The Al of stripping is as the Al source in building-up process;
TEOS is mixed with deionized water and ethanol, and after stirring, the precursor catalyst fines that adds step 1) to obtain dropwise adds template afterwards, mixes, and gets synthetic liquid, and in synthetic liquid, mol ratio is 1.0Al:5S i:8TPAOH:50EtOH:100H
2O； To synthesize afterwards liquid sealing in the stainless steel water thermal synthesis still with the polytetrafluoroethylene (PTFE) inner core, the Hydrothermal Synthesis temperature is 165 ℃, and generated time is 100h.After reaction finishes, catalyst is filtered from solution, wash to washing lotion pH value less than 8 with deionized water, ethanol, 130 ℃ of dry 10h afterwards, 500 ℃ of roasting 12h removed template methods obtain new structure PdHZSM-5 molecular sieve catalyst.
The PdHZSM-5 catalyst comprises Pd active component nano particle particle and HZSM-5 molecular sieve, described Pd active component nano particle embeds and is dispersed in the HZSM-5 molecular sieve, described Pd active component nano particle content in catalyst is 9.8wt% after testing, active Pd nano particle diameter is 7nm, and the zeolite crystal size is 4 μ m;
Gained PdHZSM-5 molecular sieve catalyst in the 10MPa lower sheeting, is got 20-40 purpose particle for the synthesis of directly aromatic hydrocarbons reactivity worth test processed of gas after pulverizing.
The activation condition of catalyst is: under normal pressure with the H of 80ml/min
2At 400 ℃ of reduction 10h.The reaction condition of catalyst is: 500 ℃, and 5.0MPa, H
2/ CO mol ratio is 2.0, W
cat/ F=5ghmol
-1, reaction result is as shown in the table.
Production has good selective the present embodiment catalyst to aromatic hydrocarbons.
Embodiment 12
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, repeats embodiment 1, and its difference only is: reactive metal is selected Cu, and the Cu load capacity is 2wt%, makes new structure CuHZSM-5 molecular sieve catalyst.
The activation condition of catalyst is: under normal pressure with the H of 80ml/min
2At 400 ℃ of reduction 10h.The reaction condition of catalyst is: 400 ℃, and 10.0MPa, H
2/ CO mol ratio is 2.0, W
cat/ F=5ghmo
-l, reaction result is as shown in the table.
Embodiment 13
A kind of active component nano particle embeds the preparation method of the catalyst of crystallization of molecular sieves, repeats embodiment 1, and its difference only is: reactive metal is selected Ni, and the Ni load capacity is 40wt%, makes new structure NiHZSM-5 molecular sieve catalyst.
Reaction result is as shown in the table.
αIso-C
5-C
12Be C
5-C
12Middle branched paraffin selective.
Embodiment 14
Repeat embodiment 1, its difference only is: reactive metal is selected Co and Pt, Co 68wt%, Pt 2wt%.Its selective effect and embodiment 13 molecular sieve catalysts approach.
Embodiment 15
Repeat embodiment 1, its difference only is: reactive metal is selected Ru and Rh, Ru 50wt% and Rh 7wt%, and its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 16
Repeat embodiment 1, its difference only is: take softex kw as template, make new structure CoMCM-41 molecular sieve catalyst.Its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 17
Repeat embodiment 1, its difference only is: take octadecylamine as template, make new structure CoHMS molecular sieve catalyst.Its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 18
Repeat embodiment 1, its difference only is: take PEO-PPOX-PEO triblock copolymer as template, make new structure CoSBA-15 molecular sieve catalyst.Its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 19
Repeat embodiment 1, its difference only is: take TMAH as template, make new structure CoHY molecular sieve catalyst.Its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 20
Repeat embodiment 1, its difference only is: do not add other materials (namely only add template and make pure silicon molecular sieve silicate-1) in Zeolite synthesis liquid, make new structure CoSilicate-1 molecular sieve catalyst.Its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 21
Repeat embodiment 1, its difference only is: be not to add the Al source in Zeolite synthesis liquid, but add the titanium source: butyl titanate (Ti (OC
4H
9)
4), make new structure CoTS-1 molecular sieve catalyst.Its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 22
Repeat embodiment 2, its difference only is: added the phosphorus source in Zeolite synthesis liquid: tributyl phosphate (OP (OCH
2CH
2CH
2CH
3)
3),, make new structure CoSAPO-34 molecular sieve catalyst.Its selective effect and embodiment 2 molecular sieve catalysts approach.
Embodiment 23
Repeat embodiment 1, its difference only is: described aluminium source is aluminum sulfate (Al
2(SO
4)
3), making new structure CoHZSM-5 molecular sieve catalyst, its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 24
Repeat embodiment 1, its difference only is: described aluminium source is aluminium chloride (AlCl
3), making new structure CoHZSM-5 molecular sieve catalyst, its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 25
Repeat embodiment 1, its difference only is: described aluminium source is aluminium isopropoxide ([(CH
3)
2CHO]
3Al), make new structure CoHZSM-5 molecular sieve catalyst, its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 26
Repeat embodiment 2, its difference only is: described silicon source is Ludox (SilicaGel), makes the CoHZSM-5 molecular sieve catalyst, and its selective effect and embodiment 2 molecular sieve catalysts approach.
Embodiment 27
Repeat embodiment 2, its difference only is: described silicon source is methyl silicate (TMeOS), makes the CoHZSM-5 molecular sieve catalyst, and its selective effect and embodiment 2 molecular sieve catalysts approach.
Embodiment 28
Repeat embodiment 2, its difference only is: described silicon source is sodium metasilicate (Na
2SiO
3), making the CoHZSM-5 molecular sieve catalyst, its selective effect and embodiment 2 molecular sieve catalysts approach.
Embodiment 29
Repeat embodiment 1, its difference only is: described titanium source is titanium tetrachloride (TiCl
4), making the CoTS-1 molecular sieve catalyst, its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 30
Repeat embodiment 1, its difference only is: described titanium source is titanyl sulfate (TiOSO
4), making the CoTS-1 molecular sieve catalyst, its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 31
Repeat embodiment 1, its difference only is: described titanium source is titanyl sulfate (TiOSO
4), making the CoTS-1 molecular sieve catalyst, its selective effect and embodiment 1 molecular sieve catalyst approach.
Embodiment 32
Repeat embodiment 2, its difference only is: described phosphorus source is phosphoric acid (H
3PO
4), making the CoSAPO-34 molecular sieve catalyst, its selective effect and embodiment 2 molecular sieve catalysts approach.
Embodiment 33
Repeat embodiment 2, its difference only is: described phosphorus source is metaphosphoric acid (HPO
3), making the CoSAPO-34 molecular sieve catalyst, its selective effect and embodiment 2 molecular sieve catalysts approach.
Obviously, the above embodiment of the present invention is only for example of the present invention clearly is described, and is not to be restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give all embodiments exhaustive.Everyly belong to the row that apparent variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (10)
1. an active component nano particle embeds the catalyst of crystallization of molecular sieves, it is characterized in that: comprise metal active constituent nano particle and molecular sieve, described metal active constituent nano particle embeds and is dispersed in molecular sieve, described metal active constituent nano particle content in catalyst is 2～70wt%, the reactive metal nano particle diameter is 4～200nm, and the zeolite crystal size is 1～10 μ m.
2. catalyst according to claim 1, it is characterized in that: preferably, described metal active constituent nano particle is one or more in following active component nano particle: Fe, Co, Ru, Cu, Pd, Ni, Rh, Pt, Mo.
3. catalyst according to claim 1 and 2, it is characterized in that: preferably, described molecular sieve be in following molecular sieve one or more: HZSM-5 molecular sieve, H beta-molecular sieve, Silicate-1 molecular sieve, MCM-41 molecular sieve, HMS molecular sieve, SBA-15 molecular sieve, HY molecular sieve, SAPO-34 molecular sieve, TS-1 molecular sieve.
4. catalyst according to claim 3, is characterized in that: preferably, also comprise auxiliary agent in catalyst.
5. catalyst according to claim 4; it is characterized in that: preferably, described auxiliary agent is one or more in oxide, reduction-state particle or the metal alloy of following element: Mn, Cu, Zr, Mg, Cr, Zn, Ce, K, Al, Ag, Pd, Pt, Ru, Rh.
6. the preparation method of the catalyst of an active component nano particle embedding crystallization of molecular sieves, is characterized in that, comprises the steps:
1) get the support type that contains silicon, aluminium, titanium, phosphorus or co-precipitated catalyst as the presoma catalyst, the presoma catalyst is pulverized, mistake 〉=20 mesh sieves get the presoma catalyst fines; Contain the metal active constituent nano particle in described presoma;
2) get silicon source, aluminium source, titanium source or phosphorus source, the mixed solution of water and ethanol dissolves, then adds template and presoma catalyst fines, stirs, and gets synthetic liquid;
3) the pH value greater than 8 condition under, synthetic liquid carries out hydrothermal synthesis reaction in the reactor of sealing; Filter after reaction, get catalyst in the middle of solid, with catalyst in the middle of deionized water or ethanol washing solid to washing lotion pH value less than 8;
4) catalyst in the middle of solid is dry under 80～150 ℃, then be heated to 350～600 ℃ of roastings, obtain product.
7. method according to claim 6, it is characterized in that: preferably, in step 1), described metal active constituent nano particle is one or more in following active component nano particle: Fe, Co, Ru, Cu, Pd, Ni, Rh, Pt, Mo.
8. according to claim 6 or 7 described methods is characterized in that: preferably, in step 1), the carrier of described presoma catalyst is to contain one or more oxide carrier of Si, Al, Ti, P.
9. method according to claim 8, it is characterized in that: preferably, in step 1), also contain builder granule in described presoma catalyst, the content of auxiliary agent in the presoma catalyst is 2～50wt%; More preferably, described auxiliary agent is one or more in oxide, reduction-state particle or the metal alloy of following element: Mn, Cu, Zr, Mg, Cr, Zn, Ce, K, Al, Ag, Pd, Pt, Ru, Rh.
10. method according to claim 8 is characterized in that: preferably, step 2) in, described silicon source is selected from one or more in following material: ethyl orthosilicate, Ludox, methyl silicate, sodium metasilicate; Described aluminium source is selected from one or more in following material: aluminum nitrate, aluminum sulfate, aluminium chloride, aluminium isopropoxide; Described titanium source is selected from one or more in following material: butyl titanate, titanium tetrachloride, titanyl sulfate; Described phosphorus source is selected from one or more in following material: tributyl phosphate, phosphoric acid, metaphosphoric acid.
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