CN103964457B

CN103964457B - A kind of SAPO molecular sieve and its production and use

Info

Publication number: CN103964457B
Application number: CN201310034594.3A
Authority: CN
Inventors: 卢旭晨; 王体壮; 闫岩
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2013-01-29
Filing date: 2013-01-29
Publication date: 2016-12-28
Anticipated expiration: 2033-01-29
Also published as: CN103964457A

Abstract

The invention discloses a kind of SAPO molecular sieve, the monocrystal of described molecular sieve is laminated structure.The aperture of described SAPO molecular sieve is moderate, has the longer life-span as methanol-to-olefins process catalyst.The invention also discloses the preparation method of described SAPO molecular sieve: with lamellar aluminosilicate as raw material, through overactivation, mixing homogenizing with phosphorus source and water and obtain wet masterbatch, drying, grinding obtain dry powder concentrate, and dry powder concentrate finally obtains the former powder of lamellar SAPO molecular sieve through distillation crystallization；Described method needs add template；Described method achieves low cost synthesis and the high value added utilization of natural lamellar aluminosilicate of SAPO molecular sieve, accelerates various material diffusion rate in molecular sieve pore passage, increases diffuser efficiency, and equipment investment is little, easy and simple to handle, beneficially environmental protection.

Description

A kind of SAPO molecular sieve and its production and use

Technical field

The present invention relates to a kind of SAPO molecular sieve and its production and use, particularly relate to a kind of lamellar SAPO molecular sieve and its production and use.

Background technology

Silicoaluminophosphamolecular molecular sieve, is also called SAPO molecular sieve, is by SiO₂、AlO₂ ^-And PO₂ ⁺Three kind four The crystal with multiple crystal structure and regular pore canal that face body is constituted.The structure species of SAPO series is a lot, According to pore size can be divided into micro-aperture structure (such as SAPO-20,25,28 etc.), small-bore structure (as SAPO-17,18,26,34,43,47 etc.), intermediate pore size structure (such as SAPO-11,31,42 etc.), Macroporous structure (such as SAPO-5,36,46 etc.) and super big hole (such as SAPO-8, VPI-5 etc.) five kinds knot Structure.

SAPO molecular sieve has variable chemical composition, adjustable acid site density and intensity, bigger ratio table Area, special pore passage structure, higher Micropore volume, excellent heat stability and hydrothermal stability, Catalytic reforming, catalytic cracking, hydrofinishing, hydroisomerization, dehydrocyclization, the hydrocarbon conversion, aromatic hydrocarbons discrimination The fields such as change have potential Development volue.Such as, SAPO-34 molecular sieve, in methanol/dimethyl ether/chloromethanes system Standby low-carbon alkene, ethylene prepare propylene, preparing ethylene by dehydrating ethanol, C₄—C₈Linear alkene cracking preparation third Alkene, oxidation of alkanes or direct dehydrogenation show excellent catalysis during preparing alkene, vehicle exhaust denitration etc. Performance；At CO₂/CH₄、CO₂/H₂And H₂/CH₄The membrane separating process of gas shows higher separation choosing Select property coefficient；It addition, also have broader development space in the field such as functional material and hydrogen storage material.Especially It is during methanol prepares alkene (MTO), the catalysis produced for catalysis material with SAPO-34 molecular sieve Agent show excellence catalysis activity and selective activization, methanol conversion up to more than 99.5%, ethylene and third Alkene total recovery is up to more than 80%, and yield of light olefins, up to more than 90%, is referred to as the optimum of MTO process Catalyst.

SAPO molecular sieve is generally with Ludox, silicic acid, white carbon, waterglass, tetraethyl orthosilicate and vapor phase method Silicon dioxide etc. are as silicon source, using boehmite, aluminum isopropylate., aluminum chloride, aluminum phosphate as aluminum source, Using phosphoric acid as phosphorus source, uniformly mix in the case of adding containing organic amine template, then use hydrothermal crystallizing Prepared by method, described hydro-thermal method prepares SAPO molecular sieve at document US 4440871；CN 92111889.9； CN 99127147.5；CN 200580033405.4；CN 200610150171.8；CN 200610152273.3； CN 200810043284.7；CN 200910076512.5；CN 200910082914.6；Topics in Catalysis 2010,53,1304；CN 201210256702.7 has reported.But, conventional hydrothermal method obtains Crystal size of molecular sieve is relatively big, and about a few micrometers is between some tens of pm, during using it as catalysis material, Greatly limit the diffusion in molecular sieve pore passage and cage of reactant and product, add reactant and product exists The time of staying in molecular sieve cage and carbon deposit chance, single pass life is shorter, and inactivation is very fast.And, routine side Method is raw materials used costly, causes molecular screen material price higher, is unfavorable for the application of molecular sieve.

Use dry gel conversion method, gas-phase reaction method or liquid phase reactor method also can prepare SAPO molecular sieve, specifically Step may is that first by the silicon source of industrial chemicals, aluminum source, phosphorus source and water, can add template, press After certain order mix and blend, (generally less than 200 DEG C) evaporating water obtains dry glue at a certain temperature, Then the aqueous solution of water or template is put into bottom reactor, above-mentioned dry glue is placed in reactor top and Do not contact with liquid water or solution, react certain time under uniform temperature self-generated pressure, i.e. obtain nanometer SAPO molecular sieve.Described method is at document CN 01135910.2；CN200710018433.X； CN201010261851.3；In CN201010551840.9 the most disclosed.The molecular sieve grain that such method obtains Spend less, reactant and product can be reduced in the diffusional resistance of molecular sieve intracell and diffusion length, thus Increase the external surface area of SAPO molecular sieve, increase diffuser efficiency, reduce SAPO molecular sieve catalyst Carbon distribution and deactivation rate.But, the silicon and aluminum source of the method is industrial chemicals, and the preparation cost of molecular sieve is higher.

CN200710176755.7 discloses a kind of utilization activation Kaolin or kaolin microsphere is prepared SAPO and divided The method of son sieve.Its step includes Kaolin roasting to obtain silicon oxide and the aluminium oxide of activity, adds phosphorus Source, template, deionized water, or add silicon source and aluminum source, aging obtain crystallization stock solution through all mixing； Crystallization stock solution being placed in reactor, carry out hydrothermal crystallizing, solid-liquid separation, solid is scrubbed, dry and de- Template processes, and obtains the SAPO molecular sieve of SAPO-34 or CHA and AEI intergrowth phase.This molecular sieve is By the sheet two-dimensional sheet material stacking that thickness is 10-200nm and the graininess three-dimensional knot grown that intersects Structure, lamella length and width is 1-10 μm, and the angle of lamella intersection growth is 60-120 degree, and sheet interlayer spacing is 5-200nm.But the SAPO molecular sieve of three dimensional particles shape structure that such method is prepared, granularity typically exists Between 4-50 μm；And the acid site density of gained molecular sieve is relatively low, acidic site intensity is relatively big, in MTO mistake Cheng Zhong, is prone to carbon deposit in this molecular sieve catalyst duct and cage, the method the granularity of the catalyst obtained and Acid properties can not reach the requirement of the MTO effective catalyst of long-life, high-low carbon olefine selective.

CN 200910046218.X discloses one and utilizes kaolin microsphere to make carrier, prepares compound in situ The method of SAPO molecular sieve, including colloid mill, spray dried after Kaolin original soil, functionalized substrate and water being mixed Dry it is shaped to kaolin microsphere, then uses the method for roasting, acidleach or alkali filter to process, thus activated Kaolin microsphere carrier；Then silicon source, aluminum source, phosphorus source, template, carrier and water mix and blend, obtain Molecular sieve mother solution；By mother solution in crystallization and solid-liquid separation under setting-out heat condition, solid is through washing, being dried Process with stripper plate and obtain compound SAPO molecular sieve.Such method explicitly points out Kaolin and activation height Ridge soil microsphere is only capable of divided active component in crystallization process and molecular sieve catalyst, improve catalyst strength, Increase catalyst wearability, reduce cost, simplify the preparation process of catalyst, function only as the effect of carrier. Silicon in Kaolin and aluminium element are not engaged in the structure of SAPO molecular sieve and build, and are not to make with Kaolin For silicon source or/and SAPO molecular sieve crystal or material are prepared in aluminum source.Prepare the cost of SAPO molecular sieve raw material Not reducing, SAPO molecular sieve catalyst carbon deposit and deactivation rate during MTO is the most very fast.

CN 201210111822.8 discloses nanometer SAPO-34 of a kind of cubic type or sheet type pattern and divides Son sieve.This molecular sieve is by aging after silicon source, aluminum source, template mix and blend, then phosphorus source and solvent is added Mixture, obtains initial gel mixture after stirring, be placed on reactor and carry out microwave heating hydrothermal crystallizing After, it is centrifuged separating, solid washing, dry, stripper plate, just obtains described cubic type or sheet type The SAPO-34 molecular sieve of pattern.The molecular sieve that such method obtains limits shape characteristic by preparation method. But large-scale microwave heating high pressure reactor investment is big, it is more difficult to realizing, maintenance and operation is complex.

Therefore, there is a need in the field to provide the SAPO molecular sieve that a kind of aperture is moderate, based on described SAPO The catalyst of molecular sieve should make reactant and product be prone to diffusion, reduces its diffusion length and diffusional resistance； And the preparation method of described SAPO molecular sieve should have low cost, feature simple to operate.

Summary of the invention

For the deficiencies in the prior art, an object of the present invention is to provide a kind of SAPO molecular sieve, base In the catalyst of described SAPO molecular sieve, having higher diffuser efficiency, catalytic life is longer.

The monocrystal of SAPO molecular sieve of the present invention is laminated structure.The sheet of monocrystal of the present invention Shape structural thickness is 10 ~ 1500nm, such as 102 ~ 680nm, 11 ~ 1000nm, 14 ~ 500nm, 13 ~ 890nm, 155 ~ 1200nm, 180 ~ 1460nm, 398 ~ 1300nm, 657 ~ 1000nm etc.；Preferably 20 ~ 700nm.

The structure of SAPO molecular sieve and acid property relationship are close, and the SAPO molecular sieve that the present invention provides is sheet Shape structure, can shorten the diffusion length of reactant and product in catalytic reaction, improves it and divides at SAPO Diffuser efficiency in son sieve reduce its in the concentration of catalytic inner and the time of staying, reduce secondary response and thick Cyclization probability, reduces carbon distribution speed, increases the life-span of catalyst, and can speed up molecular sieve catalytic The reproduction speed of agent, increases the utilization ratio of catalyst.

Preferably, the surfacing of described SAPO molecular sieve monocrystal laminated structure, described surface is polygon In shape plane, preferably triangle projective planum, quadrangular plan, pentagon plane, hexagon plane any 1 Plant or the combination of at least 2 kinds.

Described SAPO molecular sieve monocrystal laminated structure is preferably quadrangular plan laminated structure, the most excellent Select the Pedicellus et Pericarpium Trapae face laminated structure that angle is 10 ~ 170 ° on the adjacent both sides of quadrangular plan.Described Pedicellus et Pericarpium Trapae dough sheet shape is tied The angle on the adjacent both sides of structure can be 12 °, 23 °, 35 °, 48 °, 59 °, 63 °, 78 °, 95 °, 118 °, 135 °, 146 °, 167 ° etc..

The surfacing of described SAPO molecular sieve monocrystal laminated structure, the corner angle of crystal are clearly demarcated.

The chemical formula of SAPO molecular sieve of the present invention is: (Si_aAl_bP_cH_d)O₂, wherein, a, b, c, d The respectively ratio of the amount of the material of Si, Al, P, H in SAPO molecular sieve chemical formula, 0.001≤a≤0.8, 0.01≤b≤0.9,0.01≤c≤0.9,0.001≤d≤0.5, and a+b+c=1, and 4a+3b+5c+d=4.

The existence form of SAPO molecular sieve of the present invention can be single dispersing crystal form and/or the reunion bodily form Formula.The particle diameter of described molecular sieve is 10nm ~ 200 μm, such as 15 ~ 500nm, 30 ~ 900nm, 3 ~ 40 μm, 20 ~ 90 μm, 45 ~ 150 μm, 30nm ~ 3 μm, 120nm ~ 190 μm, 300nm～160 μm, 430nm ~ 185 μm Deng, preferably 10nm～100 μm.

Preferably, the specific surface area of described SAPO molecular sieve is 100 ~ 900m²/ g, such as 101 ~ 800m²/g、 137~500m²/g、148m²/g、187m²/g、239m²/g、268m²/g、288m²/g、354m²/g、389m²/g、 447m²/g、495m²/g、536m²/g、582m²/g、667m²/g、794m²/g、806m²/g、885m²/g、 879m²/ g etc..

Preferably, the pore volume of described SAPO molecular sieve is 0.05 ~ 0.8cm³/ g, such as 0.06cm³/g、 0.09cm³/g、0.12cm³/g、0.26cm³/g、0.48cm³/g、0.69cm³/g、0.75cm³/ g etc..

Preferably, the aperture of described SAPO molecular sieve is 0.3 ~ 1.0nm, such as 0.38nm, 0.42nm, 0.54nm, 0.56nm, 0.62nm, 0.73nm, 0.85nm, 0.93nm, 0.98nm etc..

Preferably, the acid site density of described SAPO molecular sieve is 0.01 ~ 0.8mmol/g, such as 0.02mmol/g、0.04mmol/g、0.12mmol/g、0.26mmol/g、0.58mmol/g、0.63mmol/g、 0.77mmol/g etc..

The two of the purpose of the present invention are to provide a kind of SAPO molecular sieve as described in one of the object of the invention Preparation method.Described method is not only able to obtain the lamellar SAPO molecular sieve that one of purpose is described, Er Qiesuo The method of stating should possess raw material be easy to get, simple to operate, yield big, usefulness is high, and low cost, free of contamination Feature.

The present invention is achieved through the following technical solutions:

The preparation method of a kind of SAPO molecular sieve, described method is with lamellar aluminosilicate as raw material, through making a living Changing, mix homogenizing with phosphorus source and water and obtain wet masterbatch, drying, grinding obtain dry powder concentrate, finally will be dry Powder concentrate obtains the former powder of lamellar SAPO molecular sieve through distillation crystallization；

Wherein, in the preparation process of described SAPO molecular sieve, it is necessary to add template；Described template Agent mixes with lamellar aluminosilicate, phosphorus source and water in mixing homogenization process；Or it is added on distillation crystallization In the solution of process, evaporate with steam and contact with dry powder concentrate and react；Or divide two by template Part is added in mixing homogenization process and distillation crystallization process respectively；

Alternatively, the former powder of lamellar SAPO molecular sieve carries out Template removal process and obtain lamellar SAPO and divide Son sieve.

The preparation method of the SAPO molecular sieve that the present invention provides uses lamellar aluminosilicate to be compound silicon and aluminum source, Not only achieve low cost synthesis and the high value added utilization of lamellar aluminosilicate of SAPO molecular sieve；And What is more important utilizes the layer structure of lamellar aluminosilicate to be template, prepares the SAPO of laminated structure Molecular sieve, provides a kind of new think of for solving MTO reactant and product diffusion problem in molecular sieve structure Road.

Alternatively, after obtaining the former powder of SAPO molecular sieve, the solution in distillation crystallization process can carry out weight Multiple utilization, carries out the preparation of the SAPO molecular sieve of next batch.

Lamellar aluminosilicate of the present invention is selected from natural lamellar aluminosilicate and synthetic stratiform aluminosilicate Salt；It preferably is selected from kaolinite race, montmorillonite race, Mica Group, pyrophillite, illite, ammonium-bearing illite, Vermiculitum With any a kind or the combination of at least 2 kinds in chlorite；Preferably kaolinite race lamellar aluminosilicate.

Preferably, described kaolinite race lamellar aluminosilicate is selected from Coaseries kaolin, hard kaolinite, soft In Kaolin, kaolinite, nacrite, dickite, galapectite and gangue any a kind or at least 2 The combination planted；Described galapectite is selected from 1.0nm galapectite and/or 0.7nm galapectite.

Preferably, described montmorillonite race lamellar aluminosilicate is selected from montmorillonite, beidellite, saponite, bentonite With any a kind or the combination of at least 2 kinds in nontronite.

Preferably, described Mica Group silicon layer shape aluminate selected from biotite, white mica, phlogopite, lepidolite, Any a kind or the combination of at least 2 kinds in ammonium Muscovitum and sericite.

It is further preferred that layered aluminosilicate is selected from natural kaolin, Coaseries kaolin, hard height Any a kind or the combination of at least 2 kinds in ridge stone, dickite, galapectite and gangue；Particularly preferably coal It is Kaolin.

The typical but non-limiting example of combination of lamellar aluminosilicate of the present invention have kaolinite/chlorite, Coaseries kaolin/montmorillonite, lepidolite/bentonite/hard kaolinite, galapectite/dickite/hard kaolinite, Coaseries kaolin/dickite/phlogopite/gangue etc..

Particle diameter≤10 μm of lamellar aluminosilicate of the present invention, such as 10nm ~ 10 μm, 13nm ~ 8 μm, 1~5μm、30nm~8μm、100nm~10μm、70nm~4μm、11~70nm、30~120nm、1~6μm、 4 ~ 9 μm etc., preferably≤2 μm, further preferred 20nm ~ 2 μm.

As the lamellar aluminosilicate of raw material, if particle diameter is excessive, in the crystallization process of SAPO molecular sieve, Silicon source is not easy diffusion, causes the silicon in lamellar aluminosilicate can not participate in building of molecular sieve structure completely, A part exists only as matrix；And in molecular sieve, silicon source is not easy dispersion and also results at molecular sieve Skeleton is formed a lot of silicon island, causes the low-density of the acidic site of molecular sieve and acid intensity high, have a strong impact on The selective catalysis performance of catalytic process, is also easy to cause carbon distribution, affects the performance of catalyst.

Distillation crystallization process of the present invention is the superjacent that dry powder concentrate is placed in distillation crystallization, and solution steams Sending out and form steam, dry powder masterbatch carries out distilling crystallization in the atmosphere that steam exists.

Preferably, the solution of described distillation crystallization is the aqueous solution containing template；Described containing template The concentration of aqueous solution is 0-99wt%, such as 0.1wt%, 0.3wt%, 0.9wt%, 1.7wt%, 7.8wt%, 14wt%、19wt%、26wt%、33wt%、39wt%、45wt%、57wt%、62wt%、69wt%、 73wt%, 78wt%, 82wt%, 87wt%, 95wt% etc., preferably 1-95wt%, further preferred 1-80wt%, Particularly preferred 20 ~ 60wt%.

The framing structure of the temperature and time of the distillation crystallization monocrystal of SAPO molecular sieve for preparing, Particle diameter, acidic site distribution etc. all have an impact.Distillation crystallization process of the present invention is carried out in hermetic container, The temperature of distillation crystallization is 160-370 DEG C such as 162 DEG C, 169 DEG C, 177 DEG C, 190 DEG C, 203 DEG C, 227 DEG C, 245 DEG C, 265 DEG C, 298 DEG C, 306 DEG C, 325 DEG C, 338 DEG C, 356 DEG C, 368 DEG C etc.；Preferably 170-350 ℃；The time of distillation crystallization preferably >=0.1h, such as 0.3h, 0.7h, 1.4h, 2.2h, 3.6h, 8h, 16h, 25h, 68h, 80h, 160h etc., further preferred 1 ~ 100d, particularly preferred 1h ~ 20d.

In distillation crystallization process, the solution of distillation crystallization can be reused, and i.e. divides as first SAPO After son sieve distillation crystallization completes, take out the former powder of SAPO molecular sieve, continue the superjacent to distillation crystallization and add Add dry powder masterbatch, carry out distilling crystallization, obtain lamellar SAPO molecular sieve.

The solution of recycling distillation crystallization decreases the loss of template, low energy consumption, and usefulness and improves, profit In environmental protection.

The SAPO molecular sieve prepared by the preparation method of SAPO molecular sieve of the present invention is had The flat crystal structure of suitable thickness, it has suitable duct and an aperture, and the density of acidic site and acidity The most controlled.In catalytic process, the diffusion rate of reactant and product is multiplied, and product is at molecular sieve cage Interior concentration is substantially reduced, and the probability that carbon distribution occurs is substantially reduced.

As one embodiment of the present invention, the preparation method of SAPO molecular sieve of the present invention include as Lower step:

(1) activation lamellar aluminosilicate；

(2) by the lamellar aluminosilicate after activation, phosphorus source and water mixing homogenizing, wet masterbatch is prepared；

(3) wet masterbatch is dried, grinds, obtain dry powder concentrate；

(4) dry powder concentrate distillation crystallization is obtained the former powder of SAPO molecular sieve；

Wherein, being also added with template in described method, described template is added on the mixing described in step (2) In homogenization process, and/or it is added in the solution of the distillation crystallization process described in step (4).

Alternatively, step (5) is carried out after step (4): former for SAPO molecular sieve powder is carried out Template removal Process, obtain SAPO molecular sieve.

Alternatively, the solution distilled in crystallization process by gained after step (4) reuses, preparation SAPO molecular sieve.Typical but non-limiting operation is: take out the SAPO molecule obtained by step (4) Sieve former powder, unreacted dry powder masterbatch is placed in distillation crystallization superjacent, closed reactor, continue into The distillation crystallization of row SAPO molecular sieve.

Preferably, in the mixing homogenization process described in step (2), auxiliary aluminum source and/or auxiliary silicon have been also added with it Source.

The template of the present invention any a kind or the combination of at least 2 kinds in organic amine and organic amine salt, Further preferably from monoethyl amine, diethylamine, triethylamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), 2-aminopropane., diisopropylamine, 1,2-dimethyl propylamine, 1,2-propane diamine, 2-allylamine, cyclopropylamine, n-butylamine, Di-n-butylamine, isobutyl amine, sec-butylamine, 1,4-butanediamine, tert-butylamine, di-iso-butylmanice, N-methylbutylamine, Amine, cyclohexylamine, 2 ethyl hexylamine, hexamethylene diamine, trioctylamine, 1,10-decamethylene diamine, distearyl amine, 1,5-diformazan Base hexylamine, monoethanolamine, diethanolamine, triethanolamine, 3-Propanolamine, monoisopropanolamine, diisopropanolamine (DIPA), Triisopropanolamine, N, N-dimethylethanolamine, N, N-diethyl ethylene diamine, triethylenediamine, Sanya second Base triamine, hexamethylenetetramine, hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, N-methylmorpholine, piperazine, aniline, diphenylamines, benzidine, o-phenylenediamine, m-diaminobenzene., p-phenylenediamine, O-toluidine, m-toluidine, open-chain crown ether, 23 dimethyl aniline, 2,4-dimethylaniline, 2,5- Dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethyl Aniline, o ethyl aniline, N-butylaniline, 2,6-diethylaniline, formanilide, to butylaniline, Monoacetylaniline, 3-aminoanisole, o-chloraniline, m-chloroaniline, parachloroanilinum, O-ethoxyl amine, M-oxethyl aniline, p-ethoxyaniline, methylphenylamine, N-ethylaniline, N, N-diethylaniline, N, accelerine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, four fourths Any a kind or the combination of at least 2 kinds in base ammonium hydroxide；Particularly preferably diethylamine, triethylamine, second two Amine, a propylamine, di-n-propylamine, tripropyl amine (TPA), 2-aminopropane., diisopropylamine, n-butylamine, di-n-butylamine, amine, Cyclohexylamine, morpholine, N-methylmorpholine, piperazine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, 4 third Any a kind or the combination of at least 2 kinds in base ammonium hydroxide, TBAH.

Template is the requisite raw material of SAPO molecular sieve preparation process, and in the present invention, template can To be added in wet masterbatch, react with other materials in wet masterbatch, effective template composition through being dried and Grinding rests in dry powder concentrate, in distillation crystallization process subsequently, plays for SAPO molecular sieve crystallization Structure directing, space are filled and the effect of charge compensation；Or template is added in distillation crystallization process Solution in, distillation crystallization solution in, template along with in solution the volatilization of solvent be dispersed in together instead Answer in device, and contact with dry powder concentrate, build for the structure of SAPO molecular sieve and play structure directing, space Fill and the effect of charge compensation.

The ratio present invention of the template added in wet masterbatch and in the solution of distillation crystallization is not particularly limited, But the quality of the template added in the solution of the mass ratio distillation crystallization of the template added in preferred wet masterbatch Greatly, the quality of the template added in further preferred wet masterbatch and the template of interpolation in the solution of distillation crystallization The mass ratio of agent is more than 0.1, less than or equal to 10, preferably greater than 1, less than or equal to 10.

It should be understood by those skilled in the art that a kind of template can guide the synthesis of several SAPO molecular sieve, According to crystallization condition and the difference of proportioning, i.e. can get single-phase SAPO molecular sieve, it is possible to obtain several The mixture of SAPO molecular sieve.Equally, a kind of SAPO molecular sieve can be guided by various template agent respectively and close Become, or guided synthesis by the mixture of various template agent.Prepared by typical but non-limiting SAPO molecular sieve The example of method selection template has: morpholine both can guide the synthesis of single-phase SAPO-34 molecular sieve, it is possible to To guide the synthesis of SAPO-5 and SAPO-34 molecular sieve mixture；Diethylamine both may be used for synthesizing single-phase The synthesis of SAPO-11, SAPO-31, SAPO-34 and SAPO-41 molecular sieve, it is also possible to guide wherein The arbitrarily synthesis of two or more mixture.Equally, diethylamine, di-n-propylamine, tetraethyl ammonium hydroxide, Morpholine, pyridine, piperidines etc. any one can guide the synthesis of SAPO-34 molecular sieve, and above-mentioned several The mixture of any two or more in template can also guide single-phase SAPO-34 molecular sieve synthesis or The generation of several SAPO molecular sieve mixture.

Preferably, any 1 during phosphorus source is selected from phosphoric acid, phosphorous acid, phosphate and organic phosphorus compound Plant or the combination of at least 2 kinds, further preferred phosphoric acid.

Typical but non-limiting phosphate include aluminum phosphate, ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, Potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium acid pyrophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, Sodium pyrophosphate, potassium phosphate, Kurrol's salt, potassium pyrophosphate, aluminum sodium phosphate, Polymeric sodium metaphosphate., hexa metaphosphoric acid Sodium, polyphosphate sodium etc.；

Typical but non-limiting organic phosphorus compound include diethylphosphate dihydro amine, triethyl phosphine acid amide, Alkyl phosphorous acid, dialkyl phosphinic acid, phenyl-phosphonic acid etc..

Described combination such as phosphoric acid/phosphorous acid, diammonium phosphate/ammonium dihydrogen phosphate/phosphorous acid, aluminum sodium phosphate/partially Sodium phosphate/sodium pyrophosphate/methylisothiouronium methylphosphite etc..

Preferably, described auxiliary aluminum source is selected from boehmite, diaspore, aluminium oxide, aluminium hydroxide, chlorine Change aluminum, aluminum nitrate, aluminum sulfate, aluminium chlorohydrate, nitric hydrate aluminum, hydrazine aluminum sulfate, aluminum phosphate, different Any a kind or the combination of at least 2 kinds in Aluminum tripropoxide and aluminate, further preferred boehmite, oxygen Change any a kind or the combination of at least 2 kinds in aluminum, aluminium hydroxide, aluminum isopropylate.；Described combination is such as intended Boehmite/aluminium hydroxide, aluminum chloride/aluminum nitrate, aluminum sulfate/aluminium oxide/boehmite, hydrazine aluminum sulfate/different Aluminum tripropoxide/nitric hydrate aluminum etc., particularly preferred boehmite.

Preferably, described auxiliary silicon source is selected from Ludox, Silica hydrogel, silicic acid, metasilicic acid, white carbon, gas Any a kind or the group of at least 2 kinds in phase method silicon dioxide, waterglass, silicate and organo-silicon compound Close；Described combination such as silicic acid/Ludox, Silica hydrogel/silicic acid/white carbon, fumed silica/Ludox/ Sodium silicate etc., any a kind or at least 2 in further preferred Ludox, fumed silica, waterglass The combination planted, particularly preferred Ludox.

SiO in wet masterbatch of the present invention₂、Al₂O₃、P₂O₅、H₂The mol ratio of O and template is (0.01-2): (0.1-1.5): (0.1-1.5): (1-500): (0-10), preferably (0.05-1.5): (0.2-1.2): (0.2-1.2): (2-400): (0.2-8).

Typical case but without limitation, in wet masterbatch, SiO₂、Al₂O₃、P₂O₅、H₂Rubbing of O and template That ratio is 0.01:0.1:0.1:1,2:1.5:1.5:500:10,1:0.8:1:200:5 or 0.4:1.4:1.2:100:6 etc..

In wet masterbatch of the present invention, SiO₂、Al₂O₃、P₂O₅、H₂The mol ratio of O and template can be led to In overly moist masterbatch, selection and the addition of each raw material calculate.

In the present invention, described activation is lived selected from calcination activation, mechanical and chemical activation, acidleach activation, alkali filter Any a kind or the combination of at least 2 kinds in change, preferably calcination activation, wet method high-energy ball milling or dry method high energy In ball milling any a kind.In activation process, the physicochemical properties of lamellar aluminosilicate change, In lamellar aluminosilicate, the reactivity of silicon and aluminum increases.

The temperature of described calcination activation preferably 600 ~ 1100 DEG C, such as 630 DEG C, 750 DEG C, 885 DEG C, 934 DEG C, 965 DEG C, 980 DEG C, 1030 DEG C, 1089 DEG C etc., the time of calcination activation preferably 0.01 ~ 100h, such as 0.02h, 0.4h, 1.8h, 2.6h, 11h, 26h, 48h, 70h, 80h, 90h etc..

Described acidleach, alkali filter, calcination activation, mechanical and chemical activation are activation method well known in the art, The present invention is no longer specifically limited.

The typical but non-limiting example of described acidleach is in the strong acid of 0.5 ~ 10.0mol/L, in room temperature ~ 100 0.1 ~ 50h is soaked at DEG C；It is the highly basic at 0.5 ~ 10.0mol/L that described alkali filters typical but non-limiting example In, at room temperature ~ 200 DEG C, lixiviation 0.1 ~ 50h.

Mixing homogenizing of the present invention selected from stirring, mixing, ball milling, ultrasonic in any a kind or at least 2 The combination planted, described combination is such as stirred and ultrasonic combination, preferably stirs and/or ultrasonic.

Preferably, described dry by any a kind in oven drying, spray drying, expansion drying mode Realize.

Preferably, described Template removal is processed as high-temperature roasting method removed template method, the temperature of described high-temperature roasting Degree be preferably 450-900 DEG C, such as 459 DEG C, 530 DEG C, 550 DEG C, 685 DEG C, 734 DEG C, 865 DEG C, 880 DEG C, 890 DEG C etc., further preferred 500 ~ 800 DEG C；The time of described high-temperature roasting preferably >=0.5h, such as 0.6h, 0.9h, 1.2h, 1.6h, 3h, 15h, 26h, 33h, 40h etc., further preferred 0.5 ~ 20h.

The atmosphere present invention of described high-temperature roasting is not particularly limited, and those skilled in the art can be according to oneself Professional knowledge and practical situation select, typical but non-limiting can be selected from air, nitrogen, helium Any a kind or the combination of at least 2 kinds in gas, argon, flue gas, carbon dioxide atmosphere.

As the preferred technical solution of the present invention, the preparation method of SAPO molecular sieve of the present invention include as Lower step:

(1) activation lamellar aluminosilicate；

(2) by the lamellar aluminosilicate after activation, phosphorus source, auxiliary aluminum source, auxiliary silicon source and water mixing homogenizing, Prepare wet masterbatch；Wherein, SiO in described wet masterbatch₂、Al₂O₃、P₂O₅、H₂O and the mol ratio of template For (0.01-2): (0.1-1.5): (0.1-1.5): (1-500): (0-10)；

(3) wet masterbatch is dried, grinds, obtain dry powder concentrate；

(4) dry powder concentrate is placed in the top of the template aqueous solution that concentration is 0-90w%, is warming up to At 160-370 DEG C, the steam of template aqueous solution is relied on to carry out distilling crystallization；Dry powder concentrate distillation crystallization is obtained To the former powder of SAPO molecular sieve；

Alternatively,

(5) former for SAPO molecular sieve powder is carried out Template removal process, obtain SAPO molecular sieve；

Alternatively,

(6) unreacted dry powder masterbatch continues to be placed in the superjacent of distillation crystallization, repeats step (4), or step (4)-(5), or step (4)-(6)；

Wherein, template aqueous solution in the content of template and step (4) in the described wet masterbatch of step (2) The content of middle template can not be 0 simultaneously.

The three of the purpose of the present invention are to provide the use of a kind of SAPO molecular sieve as described in one of the object of the invention On the way, described SAPO molecular sieve separates with gas as catalyst, catalyst carrier, adsorbent, desiccant Agent.

Preferably, to be used as catalytic reforming, catalytic cracking, hydrofinishing, hydrogenation different for described SAPO molecular sieve Catalyst during structure, dehydrocyclization, aromatic disproportion or methanol/dimethyl ether conversion or catalyst carrier；

Preferably, described SAPO molecular sieve be used as methanol/dimethyl ether prepare low carbon olefin hydrocarbon catalyst or Catalyst carrier；

Preferably, described SAPO molecular sieve is used as alkaline gas adsorbent；Preferably, described stripper plate SAPO Molecular sieve is used as the separating medium of micro-molecular gas；

Preferably, described SAPO molecular sieve is used as the carrier of cleaning catalyst for tail gases of automobiles.

Typical but non-limiting example have SAPO molecular sieve is used for low-carbon alkene be converted into gasoline series produce Thing；The dehydrocyclization of gasoline process paraffin is prepared for reformed naphtha；Isomerization for aromatic hydrocarbon Reaction；Or for methanol oxidation；Or the carrier etc. for cleaning catalyst for tail gases of automobiles.

The catalyst prepared as catalyst material, in catalytic reaction process, reactant and raw material Diffusion length is short, and mass transfer is fast, and diffuser efficiency is high, and product concentration in lattice is low, the probability of secondary response Little, the probability of the carbon distribution caused reduces, thus the lasting a long time of catalyst.

Typical but non-limiting example is: during methanol oxidation, under the effect of SAPO molecular sieve, Methanol can be catalytically conveted to the hydro carbons of C1-10, and the activity of SAPO molecular sieve is the highest in this process, turns Rate is the biggest, but occurs the probability of carbon distribution to be also greatly increased, and catalyst is very easy to inactivation；And in order to reduce The generation of carbon distribution, needing to reduce the activity of SAPO molecular sieve, i.e. reducing it acid, although so extending The activity of catalyst, but the selectivity of alkene is deteriorated by catalyst.And the SAPO molecular sieve that the present invention provides For laminated structure, not only having good catalytic performance, the acidity of acidic site is moderate simultaneously, and carbon distribution occurs Probability is little, and the life-span of catalyst is extended.

Exchange as ion, the exchange velocity of ion can be accelerated.

As adsorbent, owing to the aperture in molecular sieve is short, adsorption efficiency is high.

Compared with prior art, there is advantages that

(1) monocrystal of SAPO molecular sieve that the present invention provides is laminated structure, can with single dispersing body or Presented in aggregate, its acid bit density is high, and the acidity of acid position is moderate；And aperture is moderate, it is more suitable for anti- Answering the diffusion in molecular sieve of thing and product, diffusion length is short, and diffuser efficiency is high, dense in lattice of product Spending low, therefore the probability of product generation secondary response is the lowest, and carbon distribution significantly reduces, the longevity of catalyst Life increases；And can speed up the reproduction speed of molecular sieve catalyst, increase the utilization ratio of catalyst；

(2) present invention also by control silicone content number and degree of scatter control in SAPO molecular sieve sour The density size of property position and Acidity；

(3) present invention uses lamellar aluminosilicate to be compound silicon and aluminum source, it is achieved that the low one-tenth of SAPO molecular sieve This synthesis, the high value added utilization of lamellar aluminosilicate；

(4) present invention uses lamellar aluminosilicate to be raw material, utilizes its layer structure for template, prepares slice The SAPO molecular sieve of shape structure, solves molecular sieve pores internal diffusion problem, especially MTO catalytic reaction mistake Cheng Zhong, causes the problem that carbon distribution affects catalyst life owing to diffusion rate is low；

(4) method that the preparation method of the SAPO molecular sieve that the present invention provides uses distillation crystallization, distillation crystalline substance Solution during change can reuse, and has reached raw material lossless, low cost, low energy consumption, and usefulness Height, equipment investment is little, easy and simple to handle, beneficially environmental protection.

Accompanying drawing explanation

Fig. 1 is the process chart of lamellar SAPO molecular sieve production method described in one embodiment of the present invention；

Fig. 2 is the SEM figure of lamellar SAPO molecular sieve described in one embodiment of the present invention.

Detailed description of the invention

As one embodiment of the present invention, the preparation method bag of lamellar SAPO molecular sieve of the present invention Include following steps:

(1) activation lamellar aluminosilicate；

(3) wet masterbatch is dried, grinds, obtain dry powder concentrate；

Alternatively,

Fig. 1 is the process chart of lamellar SAPO molecular sieve production method described in present embodiment；

For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art it will be clearly understood that The only help of described embodiment understands the present invention, is not construed as the concrete restriction to the present invention.

Embodiment 1

The preparation method of a kind of lamellar SAPO molecular sieve comprises the steps:

(1) Kaolin of Suzhou (kaolinite content is 90.5%) is ground to particle mean size and is less than 0.3 μm, Activation powder must be ground；

(2) take grinding activation powder 30.0g, join in 200.0g deionized water, be hereafter separately added into 85.0% Strong phosphoric acid 52.0g, boehmite 16.4g(alumina content 78.2%), morpholine 20.0g, be stirred vigorously, Obtain wet masterbatch；In wet masterbatch, SiO₂、Al₂O₃、P₂O₅、H₂The mol ratio of O and template is 0.244:0.248:0.226:11.54:0.230；

(3) above-mentioned wet masterbatch is evaporated in 120 DEG C of baking ovens, and is ground to particle mean size less than 50 μm, To dry powder concentrate；

(4) above-mentioned dry powder concentrate 10.0g is placed in above the morpholine aqueous solution that 50mL concentration is 40.0%, Distilling crystallization 120h at 200 DEG C, cooling, the solid obtained is lamellar SAPO-34 molecular screen primary powder；

(5) lamellar SAPO-34 molecular screen primary powder is placed in Muffle furnace, with 2 DEG C/min in moving air It is warming up to 600 DEG C, is incubated 4h, carries out stripper plate process, naturally cool to room temperature, obtain Pedicellus et Pericarpium Trapae dough sheet shape SAPO-34 molecular sieve.

Gained lamellar SAPO-34 molecular sieve is carried out SEM scanning, SEM scanning figure (figure as shown in Figure 2 2 is the SEM figure of lamellar SAPO molecular sieve described in the present embodiment), it can be deduced that SAPO-34 molecular sieve Particle diameter is about 0.4 ~ 3.5 μm, and thickness is 0.1 ~ 1.5 μm, and corner is clearly demarcated, and surface is complete, and thing is mutually pure；

Langmuir method specific surface area is 772m²/ g, pore volume is 0.278cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion are less than 10%；Use NH₃-TPR measures acid site density 0.36mmol/g。

Embodiment 2

The preparation method of a kind of lamellar SAPO molecular sieve, uses embodiment 1 to prepare Pedicellus et Pericarpium Trapae dough sheet shape The solution of the distillation crystallization after SAPO-34 molecular sieve, continues dry powder concentrate (proportioning and embodiment 1 phase Together) 10.0g is placed in distillating still top, and the morpholine solution keeping distillating still bottom is the most removed, 200 DEG C of steamings Evaporating crystallization 120h, cooling, solid is Pedicellus et Pericarpium Trapae panel shape or lamellar SAPO-34 molecular screen primary powder.

Molecular screen primary powder is placed in Muffle furnace, in moving air, is warming up to 550 DEG C with 2 DEG C/min, insulation 4h, carries out stripper plate process, naturally cools to room temperature, obtains Pedicellus et Pericarpium Trapae dough sheet shape SAPO-34 molecular sieve.

Embodiment 3

The preparation method of a kind of lamellar SAPO molecular sieve, comprises the steps:

Wherein, step (1)-(3) are identical with the step of embodiment 1 (1)-(3)；

(4) dry powder concentrate 15.0g is placed in the top of the morpholine aqueous solution that 100g concentration is 90.0wt%, 200 Distilling crystallization 120h at DEG C, cooling, the solid obtained is lamellar SAPO-34 molecular screen primary powder；

(5) lamellar SAPO-34 molecular screen primary powder is placed in Muffle furnace, with 0.1 in flowing ordinary nitrogen DEG C/min is warming up to 900 DEG C, it is incubated 0.5h, carries out stripper plate process, naturally cool to room temperature, obtain Pedicellus et Pericarpium Trapae face Lamellar SAPO-34 molecular sieve.

Gained lamellar SAPO-34 molecular sieve particle diameter is about 0.5 ~ 3.5 μm, and thickness is 0.1 ~ 1.4 μm, corner Clearly, surface is complete, and thing is mutually pure；

Langmuir method specific surface area is 768m²/ g, pore volume is 0.276cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion are less than 10%；Use NH₃-TPR measures acid site density 0.31mmol/g。

Embodiment 4

Wherein, step (1)-(3) are identical with the step of embodiment 1 (1)-(3)；

(4) dry powder concentrate 2.0g is placed in the top of the morpholine aqueous solution that 100.0g concentration is 1wt%, 370 Distilling crystallization 0.1h at DEG C, cooling, the solid obtained is lamellar SAPO-34 molecular screen primary powder；

(5) lamellar SAPO-34 molecular screen primary powder is placed in tube type vacuum stove, flowing ordinary nitrogen in 0.1 DEG C/min is warming up to 900 DEG C, is incubated 0.5h, carries out stripper plate process, naturally cool to room temperature, obtain Pedicellus et Pericarpium Trapae dough sheet shape SAPO-34 molecular sieve.

Gained lamellar SAPO-34 molecular sieve is carried out SEM scanning, it can be deduced that SAPO-34 molecular sieve Particle diameter is about 0.1 ~ 1.0 μm, and thickness is 0.05 ~ 0.5 μm, and corner is clearly demarcated, and surface is complete.

Langmuir method specific surface area is 172m²/ g, pore volume is 0.035cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion are less than 10%；Use NH₃-TPR measures acid site density 0.1mmol/g。

Embodiment 5

(1) Inner Mongol Coaseries kaolin (kaolinite content is 92.6%) wet ball mill method is ground to averagely Granularity is less than 50 μm, is placed in Muffle furnace, at 600 DEG C of roasting 100h, obtains activation powder；

(2) take activation powder 50.0g to be placed in 200.0g deionized water, be subsequently to added into the strong phosphoric acid of 85.0% 52.0g, with 600r/min wet ball grinding 1h in planetary ball mill so that the aluminosilicate in wet masterbatch Mean diameter is 0.1 μm, in wet masterbatch, and SiO₂、Al₂O₃、P₂O₅、H₂The mol ratio of O and template is 0.417:0.208:0.226:11.54:0；

(3) above-mentioned wet masterbatch is spray-dried, obtains the granularity dry powder concentrate less than 200.0 μm

(4) above-mentioned dry powder concentrate 10.0g being placed in 100mL concentration is that 80.0% tetraethyl ammonium hydroxide is water-soluble Above liquid, distilling crystallization 48h at 220 DEG C, cooling, the solid obtained is lamellar SAPO-34 molecular screen primary Powder；

(5) lamellar SAPO-34 molecular screen primary powder is placed in tube furnace, with 1 DEG C/min in flowing flue gas It is warming up to 600 DEG C, is incubated 4h, carries out stripper plate process, naturally cool to room temperature, obtain Pedicellus et Pericarpium Trapae panel shape SAPO-34 molecular sieve.

Gained lamellar SAPO-34 molecular sieve is carried out SEM scanning, it can be deduced that SAPO-34 molecular sieve Particle diameter is about 0.3 ~ 3.6 μm, and thickness is 0.15 ~ 1.6 μm, and corner is clearly demarcated, and surface is complete.

Langmuir method specific surface area is 725m²/ g, pore volume is 0.235cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion are less than 10%；Use NH₃-TPR measures acid site density 0.65mmol/g。

Embodiment 6

(1) Inner Mongol Wuhai gangue (kaolinite content is 80.6%) is ground to particle mean size and is less than 100 μm, It is placed in fast fluidized bed, at 1200 DEG C of roasting 0.01h, obtains activation powder；

(2) take activation powder body 20.0g to be placed in 2000.0g deionized water, be subsequently to added into the dense phosphorus of 85.0% Acid 520.0g, aluminium oxide 230.0g, ball milling 0.2h in high energy ball mill so that the aluminosilicate in wet masterbatch The mean diameter of salt is 3 μm, in wet masterbatch, and SiO₂、Al₂O₃、P₂O₅、H₂O and the mol ratio of template For 0.073:1.164:1.128:57.72:0；

(3) above-mentioned wet masterbatch is dried at 400 DEG C in flash dryer, obtains granularity less than 200.0 μm Dry powder concentrate；

(4) above-mentioned dry powder concentrate 10.0g being placed in 100mL concentration is above 50.0% n-butylamine aqueous solution, Distilling crystallization 48h at 220 DEG C, cooling, the solid obtained is lamellar SAPO-34 molecular screen primary powder；

Gained lamellar SAPO-34 molecular sieve is carried out SEM scanning, it can be deduced that SAPO-34 molecular sieve Particle diameter is about 0.3 ~ 1.5 μm, and thickness is 0.1 ~ 1.0 μm, and corner is clearly demarcated, and surface is complete；

Langmuir method specific surface area is 472m²/ g, pore volume is 0.132cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion, less than 10%, use NH₃-TPR measures acid site density 0.11mmol/g。

Embodiment 7

(1) Anqiu, Shandong montmorillonite (smectite content is 92.0%) disintegrating machine is smashed to particle mean size little In 50 μm, it is placed in Muffle furnace, at 1200 DEG C of roasting 1h, takes roasting powder 100.0g at room temperature 500ml Concentration is leaching 50h, solid-liquid separation in 0.5mol/L hydrochloric acid, obtains solid for activation powder；

(2) take grinding activation powder body 5.0g to be placed in 100.0g deionized water, be separately added into aluminum isopropylate. 50.0g, add phosphorous acid 40.0g, diethylamine 20.0g, utilize planetary ball mill with 400r/min ball milling 4h, The mean diameter making the aluminosilicate in wet masterbatch is 8 μm, in wet masterbatch, and SiO₂、Al₂O₃、P₂O₅、 H₂The mol ratio of O and template is 0.083:0.245:0.244:5.555:0.273；

(3) by above-mentioned wet masterbatch in ventilated drying oven at 150 DEG C dried, mortar grinder is less than to granularity The dry powder concentrate of 100.0 μm；

(4) above-mentioned dry powder concentrate 10.0g is placed in that 100mL concentration is 30.0% diethylamine and 20.0% three Above ethamine mixed aqueous solution, distilling crystallization 72h at 220 DEG C, cooling, the solid obtained is lamellar SAPO-34 molecular screen primary powder；

(5) lamellar SAPO-34 molecular screen primary powder is placed in tube furnace, with 1 DEG C in the common argon that flows / min is warming up to 600 DEG C, is incubated 5h, carries out stripper plate process, naturally cool to room temperature, obtain Pedicellus et Pericarpium Trapae panel Shape SAPO-34 molecular sieve.

Gained lamellar SAPO-34 molecular sieve is carried out SEM scanning, it can be deduced that SAPO-34 molecular sieve Face exhibition is about 0.4 ~ 2.5 μm, and thickness is 0.1 ~ 1.0 μm, and corner is clearly demarcated, and surface is complete；

Langmuir method specific surface area is 358m²/ g, pore volume is 0.124cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion, less than 10%, use NH₃-TPR measures acid site density 0.06mmol/g。

Embodiment 8

(1) by broken for In Xiazijie Region, xinjiang bentonite (crystallization is beidellite mutually, and beidellite content is 88.3%) Machine is smashed to particle mean size less than 20 μm, is placed in Muffle furnace, at 750 DEG C of roasting 2h, obtains activation powder Material；

(2) take activation powder body 10.0g to be placed in 150.0g deionized water, be separately added into phosphoric acid 30.0g, Aluminum chloride 20.0g, pyridine 30.0g, wet grinding so that the mean diameter of the aluminosilicate in wet masterbatch is 10 μm, In wet masterbatch, SiO₂、Al₂O₃、P₂O₅、H₂The mol ratio of O and template is 0.080:0.115:0.130:8.333:0.379；

(3) above-mentioned wet masterbatch is evaporated in 120 DEG C of ventilated drying ovens, and is ground to particle mean size and is less than 150 μm, obtain dry powder concentrate；

(4) above-mentioned dry powder concentrate 10.0g being placed in 50mL concentration is above 30.0% morpholine aqueous solution, 200 DEG C of distillation crystallization 120h, cooling, the solid obtained is lamellar SAPO-34 molecular screen primary powder；

(5) lamellar SAPO-34 molecular screen primary powder is placed in tube furnace, with 1 DEG C in the common argon that flows / min is warming up to 550 DEG C, is incubated 5h, carries out stripper plate process, naturally cool to room temperature, obtain Pedicellus et Pericarpium Trapae panel Shape SAPO-34 molecular sieve.

Gained lamellar SAPO-34 molecular sieve is carried out SEM scanning, it can be deduced that SAPO-34 molecular sieve Face exhibition is about 0.4 ~ 3.2 μm, and thickness is 0.1 ~ 1.8 μm, and corner is clearly demarcated, and surface is complete, and thing is mutually pure；

Langmuir method specific surface area is 785m²/ g, pore volume is 0.269cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion, less than 10%, use NH₃-TPR measures acid site density 0.4mmol/g。

Embodiment 9

(1) according to document (D E Harlov, M Andrut, BPhysics and Chemistry of Minerals.2001,28:268-276) synthesis ammonium Muscovitum, substitute heavy water described in document with deionized water and carry out crystalline substance Change reaction, obtain ammonium mica powder；Ammonium mica powder is placed in Muffle furnace, at 600 DEG C of roasting 2h, Activation powder；

(2) take activation powder 10.0g to be placed in 100.0g deionized water, be separately added into AlPO₄Powder body 50.0g, Morpholine 30.0g, is stirred vigorously, in wet masterbatch, and SiO₂、Al₂O₃、P₂O₅、H₂O and the mol ratio of template For 0.090:0.205:0.205:5.555:0.345；

(4) above-mentioned dry powder concentrate 10.0g being placed in 50mL concentration is above 30.0% diethylamine aqueous solution, Distilling crystallization 120h at 200 DEG C, cooling, the solid obtained is lamellar SAPO-34 molecular screen primary powder；

Gained lamellar SAPO-34 molecular sieve is carried out SEM scanning, it can be deduced that SAPO-34 molecular sieve Face exhibition is about 0.4 ~ 3.5 μm, and thickness is 0.1 ~ 1.5 μm, and corner is clearly demarcated, and surface is complete, and thing is mutually pure；

Langmuir method specific surface area is 756m²/ g, pore volume is 0.272cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion, less than 10%, use NH₃-TPR measures acid site density 0.5mmol/g。

Embodiment 10

(2) take grinding activation powder 30.0g, join in 200.0g deionized water, be hereafter separately added into 85.0% Strong phosphoric acid 52.0g, boehmite 16.4g(alumina content 78.2%), cyclohexylamine 30.0g, acutely stir Mix, in wet masterbatch, SiO₂、Al₂O₃、P₂O₅、H₂The mol ratio of O and template is 0.212:0.232:0.226:11.544:0.327；

(4) above-mentioned dry powder concentrate 10.0g is placed in above the Aqueous Solution of Cyclohexylamine that 50mL concentration is 60.0%, Distilling crystallization 120h at 200 DEG C, cooling, the solid obtained is lamellar SAPO-44 molecular screen primary powder；

(5) lamellar SAPO-44 molecular screen primary powder is placed in Muffle furnace, with 2 DEG C/min in moving air It is warming up to 600 DEG C, is incubated 4h, carries out stripper plate process, naturally cool to room temperature, obtain Pedicellus et Pericarpium Trapae dough sheet shape SAPO-44 molecular sieve.

Gained lamellar SAPO-44 molecular sieve is carried out SEM scanning, it can be deduced that SAPO-44 molecular sieve Face exhibition is about 0.4 ~ 5.5 μm, and thickness is 0.2 ~ 2.0 μm, and corner is clearly demarcated, and surface is complete, and thing is mutually pure；

Langmuir method specific surface area is 782m²/ g, pore volume is 0.275cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion, less than 10%, use NH₃-TPR measures acid site density 0.6mmol/g。

Embodiment 11

(2) take grinding activation powder 30.0g, join in 200.0g deionized water, be hereafter separately added into 85.0% Strong phosphoric acid 52.0g, boehmite 16.4g(alumina content 78.2%), N-methylbutylamine 50.0g, acute Strong stirring, in wet masterbatch, SiO₂、Al₂O₃、P₂O₅、H₂The mol ratio of O and template is 0.212:0.232:0.226:11.544:0.573；

(4) above-mentioned dry powder concentrate 10.0g is placed in the N-methylbutylamine aqueous solution that 50mL concentration is 50.0% Top, distills crystallization 5d at 200 DEG C, and cooling, the solid obtained is lamellar SAPO-47 molecular screen primary Powder；

(5) lamellar SAPO-47 molecular screen primary powder is placed in Muffle furnace, with 2 DEG C/min in moving air It is warming up to 600 DEG C, is incubated 4h, carries out stripper plate process, naturally cool to room temperature, obtain Pedicellus et Pericarpium Trapae dough sheet shape SAPO-47 molecular sieve.

Gained lamellar SAPO-47 molecular sieve is carried out SEM scanning, it can be deduced that SAPO-47 molecular sieve Face exhibition is about 0.4 ~ 5.5 μm, and thickness is 0.2 ~ 2.0 μm, and corner is clearly demarcated, and surface is complete, and thing is mutually pure；

Langmuir method specific surface area is 782m²/ g, pore volume is 0.275cm³/ g, aperture is 0.3 ~ 0.5nm, Mesoporous, macropore and external surface area proportion, less than 10%, use NH₃-TPR measures acid site density 0.37mmol/g。

Comparative example 1

With CN01135910.2 disclosed embodiment 7 for comparative example 1.

Comparative example 2

With CN200710176755.7 disclosed embodiment 14 for comparative example 2.

Comparative example 3

With CN200910046218.X disclosed embodiment 2 for comparative example 3.

Catalytic performance is tested:

It is 1:1 with 100 mesh quartz sands according to mass ratio respectively by the SAPO molecular sieve described in embodiment 1-10 Mixed grinding, compressing, pulverize, take 10 ~ 100 mesh sample MTO process catalyst, at 450 DEG C Under, with normal pressure high-purity N₂Make carrier gas, the methanol solution that weight/mass percentage composition is 25% is pumped into reactor.When With mass space velocity as 1.0h^-1During reaction, the conversion ratio of methanol reaches the life-span of the catalyst of more than 90%, test Result is as shown in table 1.

Table 1 catalytic performance test result

Embodiment	Catalyst life (h)	Embodiment	Catalyst life (h)
				1	16.0	7	16.0
2	14.0	8	14.0
				3	18.0	9	13.5
4	3.0	Comparative example 1	4.5
				5	17.0	Comparative example 2	6.0
6	16.5	Comparative example 3	8.0

As can be seen from Table 1, the SAPO that the embodiment of the present invention 1,2,3,5,6,7,8,9 provides divides Son sieve is during methanol oxidation, it is ensured that methanol conversion reaches the catalyst life of 90% and greatly improves.

Applicant states, the present invention illustrates detailed process equipment and the technique of the present invention by above-described embodiment Flow process, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention Have to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field should This understands, any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims

1. the preparation method of a SAPO molecular sieve, it is characterised in that described method is with lamellar aluminosilicate For raw material, through overactivation, mixing homogenizing with phosphorus source and water and obtain wet masterbatch, drying, grinding obtain fundatrix Material powder, finally obtains the former powder of lamellar SAPO molecular sieve by dry powder concentrate through distillation crystallization；

Wherein, in the preparation process of described SAPO molecular sieve, it is necessary to add template；Described template Agent mixes with lamellar aluminosilicate, phosphorus source and water in mixing homogenization process；Or template is divided two Divide in the solution being added on mixing homogenization process and distillation crystallization process respectively；

The monocrystal of described molecular sieve is laminated structure；

Described laminated structure be triangle projective planum laminated structure, at least one angle be the Pedicellus et Pericarpium Trapae dough sheet shape of 10～78 ° In structure, pentagon plane platelet structures, hexagon plane laminated structure any a kind or at least 2 kinds Combination；

The specific surface area of described SAPO molecular sieve is 100～900m²/g；

The pore volume of described SAPO molecular sieve is 0.05～0.8cm³/g；

The aperture of described SAPO molecular sieve is 0.3～1.0nm；

The acid site density of described SAPO molecular sieve is 0.01～0.8mmol/g.

2. preparation method as claimed in claim 1, it is characterised in that the laminated structure of described monocrystal is thick Degree is 10～1500nm.

3. preparation method as claimed in claim 2, it is characterised in that the laminated structure of described monocrystal is thick Degree is 20～1000nm.

4. preparation method as claimed in claim 1, it is characterised in that the surfacing of described laminated structure, The corner angle of crystal are clearly demarcated.

5. preparation method as claimed in claim 1, it is characterised in that the chemical formula of described molecular sieve is: (Si_aAl_bP_cH_d)O₂, wherein, 0.001≤a≤0.8,0.01≤b≤0.9,0.01≤c≤0.9,0.001≤d ≤ 0.5, and a+b+c=1,4a+3b+5c+d=4.

6. preparation method as claimed in claim 1, it is characterised in that described SAPO molecular sieve is with single point Dissipate crystal form and/or aggregate form exists.

7. preparation method as claimed in claim 1, it is characterised in that the particle diameter of described SAPO molecular sieve For 10nm～200 μm.

8. preparation method as claimed in claim 7, it is characterised in that the particle diameter of described SAPO molecular sieve For 10nm～100 μm.

9. preparation method as claimed in claim 1, it is characterised in that former by lamellar SAPO molecular sieve Powder carries out Template removal process and obtains lamellar SAPO molecular sieve.

10. preparation method as claimed in claim 1, it is characterised in that recycling distillation crystallization process In solution carry out the preparation of SAPO molecular sieve.

11. the method for claim 1, it is characterised in that described method comprises the steps:

(1) activation lamellar aluminosilicate；

(3) wet masterbatch is dried, grinds, obtain dry powder concentrate；

Wherein, being also added with template in described method, described template is added on the mixing described in step (2) In homogenization process, and it is added in the solution of the distillation crystallization process described in step (4)；Or, described mould Plate agent is only added in the mixing homogenization process described in step (2).

12. methods as claimed in claim 11, it is characterised in that carry out step (5) after step (4): Former for SAPO molecular sieve powder is carried out Template removal process, obtains SAPO molecular sieve.

13. method as claimed in claim 11, it is characterised in that crystallization will be distilled after step (4) The solution of process reuses, and prepares SAPO molecular sieve.

14. methods as claimed in claim 11, it is characterised in that the mixing homogenizing described in step (2) During, it is also added with auxiliary aluminum source and/or auxiliary silicon source.

15. the method for claim 1, it is characterised in that layered aluminosilicate is selected from natural Lamellar aluminosilicate and synthetic lamellar aluminosilicate.

16. methods as claimed in claim 15, it is characterised in that layered aluminosilicate is selected from kaolinite Appointing in stone race, montmorillonite race, Mica Group, pyrophillite, illite, ammonium-bearing illite, Vermiculitum and chlorite Anticipate a kind or the combination of at least 2 kinds.

17. methods as claimed in claim 16, it is characterised in that layered aluminosilicate is selected from kaolinite Stone race lamellar aluminosilicate.

18. methods as claimed in claim 17, it is characterised in that described kaolinite race lamellar aluminosilicate Selected from Coaseries kaolin, hard kaolinite, soft kaolin, kaolinite, nacrite, dickite, angstrom Any a kind or the combination of at least 2 kinds in Lip river stone and gangue；Described galapectite is selected from 1.0nm galapectite And/or 0.7nm galapectite.

19. methods as claimed in claim 16, it is characterised in that described montmorillonite race lamellar aluminosilicate Any a kind or the combination of at least 2 kinds in montmorillonite, beidellite, saponite, bentonite and nontronite.

20. methods as claimed in claim 16, it is characterised in that described Mica Group silicon layer shape aluminate selects In biotite, white mica, phlogopite, lepidolite, ammonium Muscovitum and sericite any a kind or at least 2 The combination planted.

21. methods as claimed in claim 16, it is characterised in that layered aluminosilicate is selected from natural In Kaolin, Coaseries kaolin, hard kaolinite, dickite, galapectite and gangue any a kind or The combination of at least 2 kinds.

22. methods as claimed in claim 21, it is characterised in that layered aluminosilicate is selected from coal measures Kaolin.

23. the method for claim 1, it is characterised in that the particle diameter of layered aluminosilicate ≤10μm。

24. methods as claimed in claim 23, it is characterised in that the particle diameter of layered aluminosilicate ≤2μm。

25. methods as claimed in claim 24, it is characterised in that the particle diameter of layered aluminosilicate is 20nm～2 μm.

26. the method for claim 1, it is characterised in that described distillation crystallization process is by fundatrix Material powder is placed in the superjacent of distillation crystallization process, and solution evaporation forms steam, and dry powder masterbatch exists at steam Atmosphere in carry out distill crystallization.

27. methods as claimed in claim 26, it is characterised in that the solution of described distillation crystallization is for containing The aqueous solution of template.

28. methods as claimed in claim 27, it is characterised in that the described aqueous solution containing template Concentration is 0-99wt%.

29. methods as claimed in claim 28, it is characterised in that the described aqueous solution containing template Concentration is 1-95wt%.

30. methods as claimed in claim 29, it is characterised in that the described aqueous solution containing template Concentration is 1-80wt%.

31. methods as claimed in claim 29, it is characterised in that the described aqueous solution containing template Concentration is 20～60wt%.

32. methods as claimed in claim 26, it is characterised in that described distillation crystallization process is in airtight appearance Carrying out in device, the temperature of distillation crystallization is 160～370 DEG C.

33. methods as claimed in claim 32, it is characterised in that the temperature of described distillation crystallization is 170-350℃。

34. methods as claimed in claim 26, it is characterised in that the time >=0.1h of described distillation crystallization.

35. methods as claimed in claim 34, it is characterised in that the time of described distillation crystallization 0.1h～100d.

36. methods as claimed in claim 35, it is characterised in that time 1h～20d of described distillation crystallization.

37. the method for claim 1, it is characterised in that SiO in described wet masterbatch₂、Al₂O₃、 P₂O₅、H₂The mol ratio of O and template is (0.01～2): (0.1～1.5): (0.1～1.5): (1～500): (0～10), template addition is not 0.

38. methods as claimed in claim 37, it is characterised in that SiO in described wet masterbatch₂、Al₂O₃、 P₂O₅、H₂The mol ratio of O and template is (0.05～1.5): (0.2～1.2): (0.2～1.2): (2～400): (0.2～8).

39. the method for claim 1, it is characterised in that described template is selected from organic amine and has Any a kind or the combination of at least 2 kinds in machine amine salt.

40. methods as claimed in claim 39, it is characterised in that described template selected from monoethyl amine, two Ethamine, triethylamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), 2-aminopropane., diisopropylamine, 1,2-bis- Methyl propylamine, 1,2-propane diamine, 2-allylamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutyl amine, Zhong Ding Amine, 1,4-butanediamine, tert-butylamine, di-iso-butylmanice, N-methylbutylamine, amine, cyclohexylamine, 2 ethyl hexylamine, Hexamethylene diamine, trioctylamine, 1,10-decamethylene diamine, distearyl amine, 1,5-dimethylhexylamine, monoethanolamine, diethanol Amine, triethanolamine, 3-Propanolamine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, N, N-dimethyl Ethanolamine, N, N-diethyl ethylene diamine, triethylenediamine, diethylenetriamine, hexamethylenetetramine, Hexamethylene imine, triethylenediamine, cyclic ethylene imines, morpholine, N-methylmorpholine, piperazine, aniline, Diphenylamines, benzidine, o-phenylenediamine, m-diaminobenzene., p-phenylenediamine, o-toluidine, m-toluidine, Open-chain crown ether, 23 dimethyl aniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethyl benzene Amine, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, o ethyl aniline, N-butyl Aniline, 2,6-diethylaniline, formanilide, to butylaniline, monoacetylaniline, 3-aminoanisole, O-chloraniline, m-chloroaniline, parachloroanilinum, O-ethoxyl amine, m-oxethyl aniline, to ethoxybenzene Amine, methylphenylamine, N-ethylaniline, N, N-diethylaniline, N, accelerine, tetramethyl hydrogen In amine-oxides, tetraethyl ammonium hydroxide, TPAOH, TBAH any a kind or The combination of at least 2 kinds.

41. methods as claimed in claim 40, it is characterised in that described template selected from diethylamine, three Ethamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), 2-aminopropane., diisopropylamine, n-butylamine, two just Butylamine, amine, cyclohexylamine, morpholine, N-methylmorpholine, piperazine, Tetramethylammonium hydroxide, tetraethyl hydrogen Any a kind or the combination of at least 2 kinds in amine-oxides, TPAOH, TBAH.

42. the method for claim 1, it is characterised in that phosphorus source selected from phosphoric acid, phosphorous acid, Any a kind or the combination of at least 2 kinds in phosphate and organic phosphorus compound.

43. methods as claimed in claim 42, it is characterised in that phosphorus source is phosphoric acid.

44. methods as claimed in claim 14, it is characterised in that described auxiliary aluminum source is selected from intending thin water aluminum Stone, diaspore, aluminium oxide, aluminium hydroxide, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminium chlorohydrate, water Close any a kind or at least 2 kinds in aluminum nitrate, hydrazine aluminum sulfate, aluminum phosphate, aluminum isopropylate. and aluminate Combination.

45. methods as claimed in claim 44, it is characterised in that described auxiliary aluminum source is selected from intending thin water aluminum Any a kind or the combination of at least 2 kinds in stone, aluminium oxide, aluminium hydroxide, aluminum isopropylate..

46. methods as claimed in claim 45, it is characterised in that described auxiliary aluminum source is boehmite.

47. methods as claimed in claim 14, it is characterised in that described auxiliary silicon source selected from Ludox, Silica hydrogel, silicic acid, metasilicic acid, white carbon, fumed silica, waterglass, silicate and organosilicon Any a kind or the combination of at least 2 kinds in compound.

48. methods as claimed in claim 47, it is characterised in that described auxiliary silicon source selected from Ludox, Any a kind or the combination of at least 2 kinds in fumed silica, waterglass.

49. methods as claimed in claim 48, it is characterised in that described auxiliary silicon source is selected from Ludox.

50. the method for claim 1, it is characterised in that described activation is selected from calcination activation, machine Any a kind or the combination of at least 2 kinds in tool chemical activation, acidleach activation, alkali filter activation.

51. methods as claimed in claim 50, it is characterised in that described activation is selected from calcination activation, wet In method high-energy ball milling or dry method high-energy ball milling any a kind.

52. methods as claimed in claim 51, it is characterised in that the temperature of described calcination activation is 600～1100 DEG C, the time of calcination activation is 0.01～100h.

53. the method for claim 1, it is characterised in that described mixing homogenizing is selected from stirring, mixing Refining, ball milling, ultrasonic in any a kind or the combination of at least 2 kinds.

54. methods as claimed in claim 53, it is characterised in that described mixing homogenizing selected from stirring and/ Or it is ultrasonic.

55. the method for claim 1, it is characterised in that described dry by oven drying, spray Mist is dried, any a kind of realization in expansion drying mode.

56. methods as claimed in claim 9, it is characterised in that described Template removal is processed as high temperature roasting Burning method removed template method.

57. methods as claimed in claim 56, it is characterised in that the temperature of described high-temperature roasting is 450-900 DEG C, time >=0.5h.

58. methods as claimed in claim 57, it is characterised in that the temperature of described high-temperature roasting is 500～800 DEG C, the time is 0.5～20h.

59. the method for claim 1, it is characterised in that described method comprises the steps:

(1) activation lamellar aluminosilicate；

(2) by the lamellar aluminosilicate after activation, phosphorus source, auxiliary aluminum source, auxiliary silicon source and water mixing homogenizing, Prepare wet masterbatch；Wherein, SiO in described wet masterbatch₂、Al₂O₃、P₂O₅、H₂O and the mol ratio of template For (0.01-2): (0.1-1.5): (0.1-1.5): (1-500): (0-10), template addition is not 0；

(3) wet masterbatch is dried, grinds, obtain dry powder concentrate；

(4) dry powder concentrate is placed in the top of the template aqueous solution that concentration is 0-90w%, is warming up to At 160-370 DEG C, rely on the steam of template aqueous solution to carry out distilling crystallization, obtain the former powder of SAPO molecular sieve.

60. methods as claimed in claim 59, it is characterised in that carrying out (5) after step (4) will The former powder of SAPO molecular sieve carries out Template removal process, obtains SAPO molecular sieve.

61. methods as described in claim 59 or 60, it is characterised in that step (4) or (5) it After carry out (6) unreacted dry powder masterbatch continue to be placed in the superjacent of distillation crystallization, repeat step (4), or step (4)-(5), or step (4)-(6)；

Wherein, in the described wet masterbatch of step (2), the content of template can not be 0.