CN104174434B - A kind of n-butene isomerization catalyst and preparation method thereof - Google Patents
A kind of n-butene isomerization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of n-butene isomerization catalyst, with there is multistage pore canal SAPO-11/SAPO-46 composite molecular screen for carrier, with noble metal for active component.The preparation method that present invention also offers above-mentioned catalyst, including passing through to control the proportioning of raw material in building-up process, and adopt suitable crystal pattern and crystallization temperature to prepare SAPO-11/SAPO-46 composite molecular screen, then carried noble metal (such as palladium or ruthenium) so that this catalyst becomes the bifunctional catalyst with metal and acid site.This preparation method is easy, and cost is low, is suitable for industrialized production.Catalyst provided by the present invention has higher catalysis activity when preparing isobutene. for n-butene skeletal isomerization, and the selectivity of the target product obtained is up to 99%.
Description
Technical field
The present invention relates to olefin isomerization catalyst field, be specifically related to a kind of n-butene isomerization catalyst and preparation method thereof.
Background technology
Isobutene. is a kind of important Organic Chemicals, is mainly used to produce the multiple Organic chemical products such as methyl tertiary butyl ether(MTBE) (MTBE), the tert-butyl alcohol, butyl rubber, polyisobutylene, methyl methacrylate, tert-butyl mercaptan.In recent years, owing to the demand of isobutene. sharply increases, the demand being particularly used for production environment friendly gasoline additive MTBE rapidly increases in the world, and the isobutene. yield that traditional oil Deep Catalytic Cracking process obtains is far from meeting industrial requirement, therefore extensively carry out the research and development of isobutene. production new technology both at home and abroad.
In twentieth century the seventies and eighties, the n-butene isomerization catalyst developed in the world is mainly and adds the acidic oxidation Al catalysts that halogenide and Si oxide obtain.Since nineteen nineties, external each major oil companies develop zeolite-type molecular sieves or non-zeolitic molecular sieves one after another as n-butene skeletal isomerisation catalyst.Catalysis material used has SAPO (SAPO) molecular sieve analog, ZSM-5, ZSM-22, ZSM-23, ZSM-35 molecular sieve, modenite, beta-zeolite etc..These molecular sieve catalyst reaction temperatures low (300-400 DEG C), slowly, stability is better, and the selectivity of isobutene. is also high for catalyst coking, inactivation；To industrialization also without using moving bed, fluidized-bed reactor, required fixing bed switching number of reactors is also few than by the situation of the catalyst that aluminium oxide is carrier, so greatly reduces the separating difficulty of the investment to process units and product.Especially SAPO molecular sieve analog, owing to it has suitable acid site distribution and special pore structure and other features, its performance is more prominent, becomes the focus of external each major company research.
SAPO molecular sieve analog is the novel non-zeolitic molecular sieves of class that U.S. combinating carbide company releases for 1984.SAPO-n is replaced AlPO by Si atom4After P or Al atom in-n skeleton formed by AlO4、PO4And SiO4The non-neutral framework of molecular sieve that tetrahedron is constituted, therefore has tradable cation, and has Bronsted acidity.The aperture of SAPO-n type molecular sieve is 0.3-0.8nm simultaneously, almost includes whole pore diameter ranges of zeolite molecular sieve；Pore volume (the H of SAPO-n type molecular sieve2O) for 0.18-0.48cm3/ g.As generation novel molecular sieve, SAPO-n type molecular sieve is in widespread attention in catalytic field.SAPO-11 molecular sieve, as a member in SAPO-n type molecular sieves, belongs to mesoporous molecular sieve, has 10 ring ellipse ducts of the non-crossing of three-dimensional, and aperture is 0.39 × 0.64nm.It is reported, SAPO-11 molecular sieve is at present at catalytic cracking, hydrogenation cracking, isomerization, studied widely with in the multiple oil refining such as the alkylation of side chain aromatic hydrocarbons, isomerization dewaxing and light olefin polymerization and chemical engineering industry or applied.
The preparation method that patent CN1283668A discloses the molecular sieve carried catalyst of a kind of SAPO-11, adopting phosphoric acid or aluminum phosphate is phosphorus source, Ludox or solid silicone are silicon source, boehmite, aluminum phosphate, aluminum isopropylate., hydrated alumina or aluminium hydroxide are aluminum source, di-n-propylamine, diisopropylamine or their mixture are organic formwork agent, SAPO-11 molecular sieve is synthesized by hydrothermal synthesis method, then the compound of load P d or Pt or both mixture obtain molecular sieve carried catalyst, and this catalyst is used for hydroisomerization reaction of alkane, test result indicate that its isomerisation selectivity and isomerization product yield significantly improve.
Summary of the invention
The invention provides a kind of with novel SAPO-11/SAPO-46 composite molecular screen for carrier, the Catalysts and its preparation method being active component with the noble metal such as palladium and ruthenium.The carrier S APO-11/SAPO-46 composite molecular screen that catalyst provided by the invention uses contains multistage pore canal, has good catalytic performance；The noble metal of load such as palladium makes catalyst have metal and acid site is difunctional, and therefore this catalyst has higher catalysis activity in n-butene isomerization reaction, and isomerization target product has higher selectivity.
According to the present invention, it is provided that a kind of n-butene isomerization catalyst, with SAPO-11/SAPO-46 composite molecular screen for carrier, with noble metal for active component.Described noble metal can be exist with precious metal simple substance form and/or the compound form containing precious metal element.
In the present invention, term " SAPO-11/SAPO-46 composite molecular screen " refers to the complex type molecular sieve of the structure with SAPO-11 molecular sieve and SAPO-46 molecular sieve.
In catalyst provided by the invention, based on the gross weight gauge of described catalyst, the content of carrier is 95.0-99.9 weight %, and the content of active component is calculated as 0.1-5.0 weight % with precious metal atom.
Above-mentioned noble metal is preferably platinum group metal, more preferably one or more in ruthenium, platinum and palladium, more preferably palladium.
Preferably, with molar basis Al in SAPO-11/SAPO-46 composite molecular screen2O3:P2O5:SiO2=1:0.5-2.5:0.2-2.0, it is preferable that Al2O3:P2O5:SiO2=1:0.8-1.0:0.2-1.0。
In the X-ray powder diffraction spectrogram of SAPO-11/SAPO-46 composite molecular screen prepared according to the methods of the invention, it is 8.1 °-8.3 °, 9.3 °-9.5 °, 13.1 °-13.3 ° at 2 θ, and characteristic peak all occur in 6.5 °-6.7 °, 7.6 °-7.8 ° and 19.8 °-20.0 ° places.
The preparation method that present invention also offers n-butene isomerization catalyst as above, including: step I: configuration concentration is 0.01-0.4mol/L, the aqueous solution being preferably the soluble precious-metal salt of 0.05-0.1mol/L；Step II: be placed in the solution that step I obtains by the SAPO-11/SAPO-46 composite molecular screen after molding, mixes 1-24 hour at 50-90 DEG C；Step III: the reactant mixture of step II is filtered, washing, then dry.
Soluble precious-metal salt in step I can be one or more in solubility palladium salt, solubility ruthenium salt and solubility platinum salt, preferably one or more in Palladous chloride., dichloro four ammonia palladium, ruthenic chloride and platinum chloride, it is particularly preferred that for Palladous chloride. and/or dichloro four ammonia palladium.In step II, it is preferable that will be equipped with the container of reactant mixture and be placed in the shaking bath of 50-100 DEG C and place 1-24 hour.The baking temperature of step III is preferably 80-120 DEG C.
In one embodiment, said method also includes the preparation process of SAPO-11/SAPO-46 composite molecular screen, including: step i): aluminum source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloid admixture, wherein with molar basis Al in described colloidal mixture2O3:R:P2O5:SiO2:H2O=1:0.2-5.0:0.6-2.0:0.1-1.5:15-80, it is preferable that Al2O3:R:P2O5:SiO2:H2O=1:2.0-3.0:0.8-1.0:0.8-1.0:30-50, wherein R is organic formwork agent；Step is ii): the colloidal mixture crystallization obtained by step i), is then washed by crystallization product, dry, and roasting is extruded.
The aluminum source, silicon source, phosphorus source and the organic formwork agent that use in the inventive method are conventional.Aluminum source is preferably one or more in aluminium hydroxide, hydrated alumina (such as boehmite), aluminum isopropylate., aluminum nitrate, aluminum sulfate and aluminum phosphate.Phosphorus source is preferably one or both in phosphoric acid and phosphorous acid.Organic formwork agent is preferably one or more in di-n-propyl amine, diisopropylamine and diethylamide.Silicon source is preferably one or more in White Carbon black, tetraethyl orthosilicate, solid silicone and Ludox.
In a preferred embodiment of the inventive method, phosphorus source used is phosphoric acid, and aluminum source is boehmite, and silicon source is Ludox, and organic formwork agent is di-n-propyl amine.
After obtaining colloidal mixture, it is preferable that this mixture is carried out aging.Therefore, the method of the present invention can further include, before step is ii), the colloidal mixture that step i) obtains carried out aging step, and wherein aging temperature is 80-130 DEG C, it is preferred to 80-110 DEG C, the aging time is 1-6 hour, it is preferred to 2-6 hour.Carry out 2-6 hour at the temperature of 80-110 DEG C it is particularly preferred that aging.
Step crystallization ii) carries out advantageous by hydrothermal crystallizing, generally carries out in hermetic container.The crystallization temperature of hydrothermal crystallizing and time are conventional.Typically, crystallization temperature is 100-200 DEG C, it is preferred to 150-200 DEG C, more preferably 180-200 DEG C, and pressure is self-generated pressure (when namely reacting in hermetic container produced pressure), and crystallization time is 1-24 hour, it is preferred to 2-24 hour.It is particularly preferred that hydrothermal crystallizing carries out 2-24 hour at the temperature of 180-200 DEG C and self-generated pressure.
Step ii) in, dry and roasting is conventional.Dry temperature is preferably 80-130 DEG C, more preferably 110-130 DEG C.Drying time is generally 2-48 hour, it is preferred to 2-24 hour.The temperature of roasting is preferably 500-600 DEG C, more preferably 550-600 DEG C.Roasting time is generally 2-12 hour, it is preferred to 3-10 hour.This roasting can carry out in Muffle furnace.Experiment finds, in the SAPO-11/SAPO-46 composite molecular screen prepared according to the method for present invention X-ray powder diffraction spectrogram before and after roasting, the number of characteristic diffraction peak and position are almost without changing.
Before being used for preparing catalyst, generally by extruded for the SAPO-11/SAPO-46 composite molecular screen carrier that obtained by above-mentioned steps.Specifically such as it is mixed with binding agent, extruded moulding, dry, pulverize and sieve, obtain the catalyst carrier of a certain size (being generally 20-40 order in the present invention).Binding agent is the traditional binders preparing catalyst, for instance hydrated alumina.
Washing step involved in the methods of the invention, it is conventional, generally can use the washing methods such as filtration washing, centrifuge washing, it is preferable that use centrifuge washing.
Present invention also offers a kind of catalyst prepared by said method and prepare the application in isobutene reaction at n-butene isomerization.The preferred isomerized reaction temperature of described n-butene is 300-450 DEG C, and reaction pressure is normal pressure, and the mass space velocity of raw material n-butene is 1.0-2.0h-1。
In the method preparing SAPO-11/SAPO-46 composite molecular screen supported catalyst of the present invention, by controlling the proportioning of raw material in building-up process, and adopt suitable crystal pattern and crystallization temperature to prepare SAPO-11/SAPO-46 composite molecular screen, shorten crystallization time, the product degree of crystallinity prepared is high, simultaneously by carried noble metal (such as palladium) so that this catalyst becomes the bifunctional catalyst with metal and acid site.
The experiment proved that, prepared according to the methods of the invention be carrier with the SAPO-11/SAPO-46 composite molecular screen with multi-stage artery structure loaded catalyst there is higher catalysis activity when preparing isobutene. for n-butene skeletal isomerization, the target product obtained has higher selectivity.Meanwhile, preparation method provided by the invention is easy, and cost is low, is suitable for industrialized production.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of the SAPO-11/SAPO-46 composite molecular screen that embodiment 1 prepares.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but scope of invention is not limited to these embodiments.
In the examples below, the structure of the SAPO-11/SAPO-46 composite molecular screen prepared by the inventive method is identified by X-ray diffraction spectrum figure.The instrument adopted is power & light company of U.S. ARLX ' TRA type diffractometer, is specifically 35kV at x-ray tube voltage, and electric current is 30mA, and sweep limits is 3-40 °, and sample is carried out qualitative analysis when being 2 °/min by scanning speed.
The microreactor used in each embodiment is tubular fixed-bed reactor, and its internal diameter is 9mm, and capacity is 25ml, and device pipeline all adopts stainless steel pipe, and catalyst loads in reactor flat-temperature zone with fixing bed form, two ends filling quartz sand.
Embodiment 1
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Weigh 9.52g(0.07mol) boehmite, it is dissolved in 10g deionized water and is made into boehmite aqueous solution, stir 0.5h.Instill 16.14g(0.14mol with vigorous stirring wherein) H3PO4(85 weight % aqueous solution), is stirred for 1h.Measuring 4.78ml(0.035mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then 10.08g(0.042mol is weighed again) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, with molar basis Al in this colloid admixture2O3:R:P2O5:SiO2:H2O=1:0.5:1:0.6:50, wherein R is di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation at 80 DEG C of aging 4h, then heat to 180 DEG C, at autogenous pressures hydrothermal crystallizing 22h.Being cooled down by crystallization products therefrom, centrifuge washing, then in 120 DEG C of dry 12h.Obtaining SAPO-11/SAPO-46 composite molecular screen, its X-ray powder diffraction figure is as shown in Figure 1.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in Muffle furnace in 550 DEG C of roasting 4h, then mixes with boehmite (as binding agent), extruded moulding, in 120 DEG C of dry 8h, pulverize and sieve, obtain the catalyst carrier of 20-40 order.
2) preparation of catalyst
The palladium chloride aqueous solution of preparation 0.01mol/L, weigh appropriate above-mentioned carrier and be placed in the solution (20ml) prepared, place 12 hours in the shaking bath of 100 DEG C, filter, the solid deionized water wash that will obtain, dry at 120 DEG C, obtain loaded catalyst, wherein based on overall catalyst weight gauge, the content of palladium is 0.2 weight %.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, with mixing carbon four unstrpped gas after ether, (" after ether mix carbon four unstrpped gas " used in the present invention refers to the residue after isobutene. is synthesized in the reactant mixture that methyl tertiary butyl ether(MTBE) obtains taking-up methyl tertiary butyl ether(MTBE) with methanol and mixes C-4-fraction, it is mainly composed of n-butene and iso-butane, its content respectively 25 volume % and 35 volume %) it is evaluated.Reaction temperature is 320 DEG C, and the mass space velocity mixing carbon four unstrpped gas after ether is calculated as 1.0h with n-butene-1.The n-butene conversion obtained is 45%, and selective isobutene is 95%.
Embodiment 2
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Weigh 9.52g(0.07mol) boehmite, it is dissolved in 10g deionized water and is made into boehmite aqueous solution, stir 0.5h.Instill 16.14g(0.14mol with vigorous stirring wherein) H3PO4(85 weight % aqueous solution), is stirred for 1h.Measuring 7.64ml(0.056mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then 10.08g(0.042mol is weighed again) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, with molar basis Al in this colloid admixture2O3:R:P2O5:SiO2:H2O=1:0.8:1:0.6:40, wherein R is di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation at 100 DEG C of aging 3h, then heat to 180 DEG C, at autogenous pressures hydrothermal crystallizing 12h.Crystallization products therefrom is cooled down, centrifuge washing, then in 110 DEG C of dry 12h, obtain SAPO-11/SAPO-46 composite molecular screen.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in Muffle furnace in 550 DEG C of roasting 4h, then mixes with boehmite (as binding agent), extruded moulding, in 120 DEG C of dry 8h, then pulverize and sieve, obtain the catalyst carrier of 20-40 order.
2) preparation of catalyst
The palladium chloride aqueous solution of preparation 0.05mol/L, weigh appropriate above-mentioned carrier and be placed in the solution (20ml) prepared, place 12 hours in the shaking bath of 100 DEG C, filter, the solid deionized water wash that will obtain, dry at 120 DEG C, obtain loaded catalyst, wherein based on overall catalyst weight gauge, the content of palladium is 1.0 weight %.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, be evaluated with mixing carbon four unstrpped gas after ether.Reaction temperature is 340 DEG C, and the mass space velocity mixing carbon four unstrpped gas after ether is calculated as 1.0h with n-butene-1.The n-butene conversion obtained is 46%, and selective isobutene is 98%.
Embodiment 3
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Weigh 9.52g(0.07mol) boehmite, it is dissolved in 10g deionized water and is made into boehmite aqueous solution, stir 0.5h.Instill 16.14g(0.14mol with vigorous stirring wherein) H3PO4(85 weight % aqueous solution), is stirred for 1h；Measuring 14.3ml(0.105mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then 13.44g(0.056mol is weighed again) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, with molar basis Al in this colloid admixture2O3:R:P2O5:SiO2:H2O=1:1.5:1:0.8:50, wherein R is di-n-propyl amine.
By the colloidal mixture of above-mentioned preparation at 110 DEG C of aging 4h, then heat to 180 DEG C, at autogenous pressures hydrothermal crystallizing 8h.Crystallization products therefrom is cooled down, centrifuge washing, then in 120 DEG C of dry 6h, obtain SAPO-11/SAPO-46 composite molecular screen.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in Muffle furnace in 600 DEG C of roasting 4h, then mixes with boehmite (as binding agent), extruded moulding, in 120 DEG C of dry 8h, then pulverize and sieve, obtain the catalyst carrier of 20-40 order.
2) preparation of catalyst
The palladium chloride aqueous solution of preparation 0.1mol/L, weigh appropriate above-mentioned carrier and be placed in the solution (20ml) prepared, place 12 hours in the shaking bath of 100 DEG C, filter, the solid deionized water wash that will obtain, dry at 120 DEG C, obtain loaded catalyst, wherein based on overall catalyst weight gauge, the content of palladium is 2.0 weight %.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, be evaluated with mixing carbon four unstrpped gas after ether.Reaction temperature is 380 DEG C, and the mass space velocity mixing carbon four unstrpped gas after ether is calculated as 1.0h with n-butene-1.The n-butene conversion obtained is 48%, and selective isobutene is 99%.
Embodiment 4
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Specific experiment operating process is roughly the same with the step 1) of embodiment 1, is different in that, the quantitative change of the di-n-propyl amine used becomes 1.91ml (0.014mol), with molar basis Al in the colloidal mixture obtained2O3:R:P2O5:SiO2:H2O=1:0.2:1:0.6:50。
2) preparation of catalyst
Specific experiment operating process and the step 2 of embodiment 1) roughly the same, it is different in that and Palladous chloride. is replaced to ruthenic chloride, based on overall catalyst weight gauge in the catalyst obtained, the content of ruthenium is 0.2 weight %.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, be evaluated with mixing carbon four unstrpped gas after ether.Reaction temperature is 400 DEG C, and the mass space velocity mixing carbon four unstrpped gas after ether is calculated as 1.5h with n-butene-1.The n-butene conversion obtained is 52%, and selective isobutene is 99%.
Embodiment 5
1) preparation of SAPO-11/SAPO-46 composite molecular screen
Weigh 9.52g(0.07mol) boehmite, it is dissolved in 10g deionized water and is made into boehmite aqueous solution, stir 0.5h.Instill 16.14g(0.14mol with vigorous stirring wherein) H3PO4(85 weight % aqueous solution), is stirred for 1h.Measuring 19.1ml(0.14mol) di-n-propyl amine is added drop-wise in above-mentioned solution, stirs 1h.Then 15.12g(0.063mol is weighed again) Ludox joins in above-mentioned solution.Add water, stir 1h, obtain colloidal mixture, with molar basis Al in this colloid admixture2O3:R:P2O5:SiO2:H2O=1:2.0:1:0.9:50, wherein R is di-n-propyl amine.
The colloidal mixture of above-mentioned preparation is warming up to 190 DEG C under air-tight state, hydrothermal crystallizing 21h at autogenous pressures.Crystallization products therefrom is cooled down, centrifuge washing, then in 130 DEG C of dry 12h, obtain SAPO-11/SAPO-46 composite molecular screen product.
The SAPO-11/SAPO-46 composite molecular screen of gained is placed in Muffle furnace in 600 DEG C of roasting 4h, then mixes with boehmite (as binding agent), extruded moulding, in 120 DEG C of dry 8h, then pulverize and sieve, obtain the catalyst carrier of 20-40 order.
2) preparation of catalyst
Specific experiment operating process and the step 2 of embodiment 3) identical.
3) catalyst application in n-butene isomerization reaction
Take the above-mentioned catalyst prepared of 2.0g and put in microreactor, be evaluated with mixing carbon four unstrpped gas after ether.Reaction temperature is 380 DEG C, and the mass space velocity mixing carbon four unstrpped gas after ether is calculated as 1.0h with n-butene-1.The n-butene conversion obtained is 46%, and selective isobutene is 95%.
As shown in Figure 1,2 θ are the characteristic peak that 8.2 °, 9.4 ° and 13.2 ° etc. all occur in that SAPO-11,2 θ are the characteristic peak that 6.6 °, 7.7 ° and 19.9 ° etc. all occur in that SAPO-46, it was shown that the composite molecular screen that embodiment 1 obtains has SAPO-11 molecular sieve and the architectural feature of SAPO-46 molecular sieve simultaneously.Additionally, find in experimentation, the composite molecular screen that the composite molecular screen of embodiment 2-5 and embodiment 1 obtain has identical structure.
From above example, adopt SAPO-11/SAPO-46 composite molecular screen to be carrier according to the present invention, in n-butene isomerization reaction, obtain the selectivity of the target product isobutene. up to 99% with the catalyst that precious metal palladium is active component.
Claims (18)
1. a n-butene isomerization catalyst, it is characterised in that with SAPO-11/SAPO-46 composite molecular screen for carrier, with noble metal for active component；
Wherein, the preparation process of described SAPO-11/SAPO-46 composite molecular screen includes:
Step i): aluminum source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloidal mixture, wherein with molar basis Al in described colloidal mixture2O3:R:P2O5:SiO2:H2O=1:(0.2-5.0): (0.6-2.0): (0.1-1.5): (15-80), R is organic formwork agent；
Step ii): the colloidal mixture crystallization that step i) is obtained, then crystallization product is washed, dry, roasting, extruded；Wherein said crystallization is undertaken by hydrothermal crystallizing, and crystallization temperature is 100-200 DEG C.
2. catalyst according to claim 1, it is characterised in that based on the gross weight gauge of described catalyst, the content of carrier is 95.0-99.9 weight %, and the content of active component is calculated as 0.1-5.0 weight % with precious metal atom.
3. catalyst according to claim 1 and 2, it is characterised in that described noble metal is platinum group metal.
4. catalyst according to claim 3, it is characterised in that described noble metal is one or more in ruthenium, platinum and palladium.
5. catalyst according to claim 1 and 2, it is characterised in that with molar basis Al in SAPO-11/SAPO-46 composite molecular screen2O3:P2O5:SiO2=1:(0.5-2.5): (0.2-2.0).
6. catalyst according to claim 5, it is characterised in that with molar basis Al in SAPO-11/SAPO-46 composite molecular screen2O3:P2O5:SiO2=1:(0.8-1.0): (0.2-1.0).
7. catalyst according to claim 1, it is characterized in that, in the X-ray powder diffraction spectrogram of described SAPO-11/SAPO-46 composite molecular screen, it is 8.1 °-8.3 °, 9.3 °-9.5 °, 13.1 °-13.3 ° at 2 θ, and characteristic peak all occur in 6.5 °-6.7 °, 7.6 °-7.8 ° and 19.8 °-20.0 ° places.
8. the method preparing catalyst as according to any one of claim 1-7, including:
Step I: configuration concentration is the aqueous solution of the soluble precious-metal salt of 0.01-0.4mol/L；
Step II: be placed in the solution that step I obtains by the SAPO-11/SAPO-46 composite molecular screen after molding, mixes 1-24 hour at 50-100 DEG C；
Step III: the reactant mixture of step II is filtered, washing, then dry；
Wherein, described method also includes the preparation process of described SAPO-11/SAPO-46 composite molecular screen, including:
Step i): aluminum source, phosphorus source, organic formwork agent, silicon source and water are mixed to get colloidal mixture, wherein with molar basis Al in described colloidal mixture2O3:R:P2O5:SiO2:H2O=1:(0.2-5.0): (0.6-2.0): (0.1-1.5): (15-80), R is organic formwork agent；
Step ii): the colloidal mixture crystallization that step i) is obtained, then crystallization product is washed, dry, roasting, extruded；Wherein said crystallization is undertaken by hydrothermal crystallizing, and crystallization temperature is 100-200 DEG C.
9. method according to claim 8, it is characterised in that in step I, the concentration of described soluble precious-metal salt is 0.05-0.1mol/L.
10. method according to claim 8, it is characterised in that described soluble precious-metal salt is one or more in solubility palladium salt, solubility ruthenium salt and solubility platinum salt.
11. method according to claim 10, it is characterised in that described soluble precious-metal salt is one or more in Palladous chloride., dichloro four ammonia palladium, ruthenic chloride and platinum chloride.
12. method according to claim 8, it is characterised in that in step i), with molar basis Al in described colloidal mixture2O3:R:P2O5:SiO2:H2O=1:(2.0-3.0): (0.8-1.0): (0.8-1.0): (30-50), wherein R is organic formwork agent.
13. method according to claim 8, it is characterised in that aluminum source is one or more in aluminium hydroxide, aluminum isopropylate., aluminum nitrate, aluminum sulfate and aluminum phosphate；Phosphorus source is one or both in phosphoric acid and phosphorous acid；Organic formwork agent is one or more in di-n-propyl amine, diisopropylamine and diethylamide；Silicon source is one or more in White Carbon black, tetraethyl orthosilicate, solid silicone and Ludox.
14. method according to claim 8, it is characterised in that described method is additionally included in step ii) before the step i) colloidal mixture obtained is carried out aging step, wherein aging temperature is 80-130 DEG C, and the aging time is 1-6 hour.
15. method according to claim 14, it is characterised in that aging temperature is 80-110 DEG C.
16. method according to claim 8, it is characterised in that step ii) crystallization temperature be 180-200 DEG C, pressure is self-generated pressure, and crystallization time is 1-24 hour；Step ii) in dry temperature be 80-130 DEG C, the temperature of roasting is 300-900 DEG C.
17. method according to claim 16, it is characterised in that the temperature of roasting is 500-600 DEG C.
18. the application that the catalyst that the method according to any one of-17 prepares according to Claim 8 is in n-butene isomerization reaction.
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| CN1504261A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing isobutene from normal butane and its preparation method and application |
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| US5888921A (en) * | 1995-10-25 | 1999-03-30 | Abb Lummus Global Inc. | Binary molecular sieves having a core and shell of different structures and compositions |
| CN1504261A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院大连化学物理研究所 | Catalyst for preparing isobutene from normal butane and its preparation method and application |
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