CN106185983A - The solvent-free method preparing SAPO 18 or SAPO 34 molecular sieve - Google Patents

The solvent-free method preparing SAPO 18 or SAPO 34 molecular sieve Download PDF

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CN106185983A
CN106185983A CN201610614191.XA CN201610614191A CN106185983A CN 106185983 A CN106185983 A CN 106185983A CN 201610614191 A CN201610614191 A CN 201610614191A CN 106185983 A CN106185983 A CN 106185983A
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sapo
molecular sieve
synthesis
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grams
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常娜
张延风
李猛
白璐
南贵珍
胡登
王宜慧
魏伟
黄巍
孙志强
章清
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Shanghai Advanced Research Institute of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume

Abstract

The invention discloses a kind of solvent-free quick method preparing SAPO 18 or SAPO 34 molecular sieve, comprise the steps: 1) silicon source, aluminum source, water, phosphoric acid, template, SAPO 34 molecular sieve crystal seed are mixed to get molecular sieve mother solution；2) the molecular sieve mother solution of step 1) is dried, and grind into powder；3) described powder mixes with water, and adds additive；4) crystallization synthesis SAPO 18 or SAPO 34 molecular sieve.Oil bath heating is combined by the present invention with uninanned platform, by the addition of crystal seed Yu additive, it is achieved that solvent-free Fast back-projection algorithm SAPO 18 or SAPO 34 molecular sieve.

Description

The solvent-free method preparing SAPO-18 or SAPO-34 molecular sieve
Technical field
The present invention relates to a kind of method preparing molecular sieve, the most solvent-free quick preparation SAPO-18 or SAPO- The method of 34 molecular sieves.
Background technology
Molecular sieve has orderly and homogeneous microcellular structure, adjustable acidity and the absorption property of uniqueness, in catalysis, absorption The fields such as separation are widely used.
SAPO-18 molecular sieve is the aperture silicon phosphorus aluminium profiles molecular sieve with AEI structure, and its aperture is 0.43 nanometer；SAPO- 34 molecular sieves are the aperture silicon phosphorus aluminium profiles molecular sieves with CHA structure, and its aperture is 0.38 nanometer.At methanol to olefins reaction (MTO) in, above two molecular sieve all shows the catalytic performance of excellence, and this is that natural gas, coal and biomass produce lightweight alkene Hydrocarbon provides the most promising commercial routes of one.There are many reports.Y.Li etc. are synthesized by hydrothermal method Obtain SAPO-18 and the SAPO-34 molecular sieve of multilayered structure, in MTO reacts, show long-term catalysis activity [Catalysis Today.233(2014)2–7].Additionally, the method using xerogel to convert can synthesize short grained point Son sieve crystal, its catalytic life is than the longer [Microporous of SAPO-18 and SAPO-34 molecular sieve of standard MesoporousMater.197(2014)229–236].Molecular sieve commonly used hydrothermal method synthesis at present, but molecular sieve During Hydrothermal Synthesis: (1) employs the organic formwork agent (relating to material cost problem and emission problem thereof) of costliness；(2) Employ solvent (produce waste water, reduce the utilization ratio of crystallizing kettle)；(3) Hydrothermal Synthesis the longest (energy consumption height and crystallization The utilization ratio of still is low) [Chem.Rev.102 (2002) 3615].In order to solve the problems referred to above during Hydrothermal Synthesis, Xiao Feng Receive and propose the method that many is intended to green syt molecular sieve, such as Template-free method synthesis, uninanned platform, ion thermal synthesis, micro- Ripple synthesis etc. [Chem.Rev.114 (2014) 1521-1543].
Oil bath heating is combined by the present invention with uninanned platform, by the addition of crystal seed Yu additive, it is achieved that nothing Solvent Fast back-projection algorithm SAPO-18 and SAPO-34 molecular sieve.Discharge of wastewater during wherein uninanned platform solves building-up process is asked Topic, improves the utilization ratio of crystallizing kettle simultaneously.Use oil bath quickly to heat generated time is greatly reduced, reduce energy consumption and Improve the utilization ratio of crystallizing kettle.Add while crystal seed and additive, accelerate the forming process of molecular sieve crystal, These innovative points above-mentioned are not mentioned in conventional invention arriving.
Summary of the invention
The problem that it is an object of the invention to overcome deficiency of the prior art and existence, it is provided that a kind of solvent-free preparation The method of SAPO-18 or SAPO-34 molecular sieve, to reach the purpose rapidly and efficiently synthesized, solve in prior art SAPO-18 or SAPO-34 Zeolite synthesis difficulty, generated time is long, and cost intensive, technique are loaded down with trivial details, wastage of material is many, it is relatively big to pollute, product is received Rate is low and the problem of poor repeatability.
For achieving the above object and other purposes, the present invention is achieved by the following technical solutions:
A kind of solvent-free method preparing SAPO-18 or SAPO-34 molecular sieve, comprises the steps:
1) silicon source, aluminum source, water, phosphoric acid, template, SAPO-34 molecular sieve crystal seed are mixed to get molecular sieve mother solution；
2) by step 1) molecular sieve mother solution dry, and grind into powder；
3) described powder mixes with water, and adds additive；
4) crystallization synthesis SAPO-18 or SAPO-34 molecular sieve.
Preferably, step 1) described in template be TEAOH.It is tetraethyl ammonium hydroxide.
Preferably, step 1) in, silicon source is converted into SiO2, aluminum source is converted into Al2O3, phosphoric acid is converted into P2O5Meter, SiO2、Al2O3、P2O5, template and H2The mol ratio of O is 0.05～0.8:1:0.5～3:0.1～5:10～100.Specifically, Silicon source is converted into SiO by the present invention2Time, it is to convert with the total mole number of silicon atom；Aluminum source is converted into Al2O3, be with The molal quantity of aluminum atom converts；Phosphoric acid is converted into P2O5, it is to convert with the total mole number of phosphorus atoms.
Preferably, it is converted into Al with source of aluminium2O3Quality on the basis of count, step 1) described in SAPO-34 molecular sieve brilliant The addition planted is 0.1～5wt%.It is highly preferred that source of aluminium is converted into Al2O3Quality on the basis of count, step 1) described in The addition of SAPO-34 molecular sieve crystal seed is 0.1～1wt%.It is highly preferred that source of aluminium is converted into Al2O3Quality on the basis of Meter, step 1) described in the addition of SAPO-34 molecular sieve crystal seed be 1wt%.
Preferably, step 1) in, described silicon source is Ludox, silicon aerosol, one or more in tetraethyl orthosilicate.
Preferably, step 1) in, source of aluminium is one or both in aluminium hydroxide and aluminum isopropylate..
Preferably, step 1) in, using stirring mixing during the mixing of molecular sieve mother solution, mixing time is 1 hour～3 days.
Preferably, step 2) in dry temperature in baking step be 80～85 DEG C.
Preferably, step 3) described in additive be ammonium chloride, di-n-propylamine, ammonium fluoride, ammonia, ammonium dihydrogen phosphate, 1- One or more in butyl-3-methy limidazolium salt.
Preferably, it is converted into Al with source of aluminium2O3Molal quantity on the basis of count, step 3) described in the interpolation of additive Amount is 0.1～10mol%.It is highly preferred that be converted into Al with source of aluminium2O3Molal quantity on the basis of count, step 3) described in add The addition adding agent is 0.1～4mol%.
Preferably, it is converted into Al with source of aluminium2O3Molal quantity on the basis of count, step 3) described in the addition of water be Described Al2O31～10 times of molal quantity.
Preferably, step 1) in time to select aluminum isopropylate. be aluminum source, crystallization generated time synthesizes constantly for little less than 1 SAPO-18 molecular sieve, crystallization generated time constantly synthesis SAPO-34 molecular sieve little more than 1；Step 1) in select aluminium hydroxide be During aluminum source, crystallization generated time is constantly synthesis SAPO-18 molecular sieve little less than 1, and crystallization generated time is little not less than 1 to be closed constantly Become SAPO-34 molecular sieve.
Preferably, step 4) in synthesis mode be static monitor.
Preferably, step 4) in synthesis temperature be 160～220 DEG C.
Preferably, step 4) in generated time be 10 minutes～24 hours.
Preferably, the size of SAPO-18 and the SAPO-34 molecular sieve obtained in above-mentioned low water content, low template method It it is 0.2～0.3 micron.
Oil bath heating is combined by the present invention with low water system；Add while crystal seed and additive, also high degree The degree of crystallinity that improve SAPO-18 or SAPO-34 molecular sieve.Said method of the present invention greatly reduces containing of water in raw material Amount shortens the response time, thus greatly reduces cost of material and environmental pollution, meets the requirement of Green Chemistry.And prepare SAPO-18 or SAPO-34 molecular sieve crystal size less, be rendered as flake, have greatly in fields such as catalysis, absorption Application potential.
Accompanying drawing explanation
Fig. 1 is Al in embodiment 12O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed) synthesizes The stereoscan photograph of SAPO-34 molecular sieve crystal, wherein the molecular sieve crystal generated time shown in Fig. 1 (a) is 6 hours, Fig. 1 B the molecular sieve crystal generated time shown in () is 9 hours, Fig. 1 (a), the left figure of (b) represent different times magnification respectively from right figure The Electronic Speculum figure of number, left figure is 20000 times, and right figure is 10000 times；
Fig. 2 is Al in embodiment 12O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed) synthesizes The XRD figure spectrum of SAPO-34 molecular sieve crystal；
Fig. 3 is Al in embodiment 12O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed) response time It it is the nitrogen adsorption isotherm of the SAPO-34 molecular sieve crystal of synthesis in 9 hours；
Fig. 4 is Al in embodiment 22O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The stereoscan photograph of SAPO-18 and the SAPO-34 molecular sieve crystal Cl) synthesized, wherein (a), (b) in Fig. 4, (c), Molecular sieve crystal generated time shown in (d), (e), (f), (g), (h) be respectively 10 minutes, 20 minutes, 40 minutes, 60 minutes, 120 minutes, 240 minutes, 360 minutes, 480 minutes, wherein the left figure of Fig. 4 (a) and right figure amplification be respectively 20000 times and 10000 times, Fig. 4 (b), (c), (d), (e), (f), (g), left figure and the right figure amplification of (h) be respectively 50000 times and 20000 times；
Fig. 5 is Al in embodiment 22O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The XRD figure spectrum of SAPO-18 and the SAPO-34 molecular sieve crystal Cl) synthesized；
Fig. 6 is Al in embodiment 22O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The nitrogen adsorption isotherm of SAPO-18 and the SAPO-34 molecular sieve crystal Cl) synthesized；
Fig. 7 is Al in embodiment 22O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% The Si element nuclear-magnetism curve of SAPO-18 and the SAPO-34 molecular sieve crystal NH4Cl) synthesized；
Fig. 8 is Al in embodiment 22O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The Al element nuclear-magnetism curve of SAPO-18 and the SAPO-34 molecular sieve crystal Cl) synthesized；
Fig. 9 is Al in embodiment 22O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The P element nuclear-magnetism curve of SAPO-18 and the SAPO-34 molecular sieve crystal Cl) synthesized；
Figure 10 is Al in embodiment 32O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The stereoscan photograph of the SAPO-18 molecular sieve crystal Cl) synthesized, wherein the molecular sieve shown in Figure 10 (a), (b), (c) is brilliant Body synthesis temperature is respectively 180 DEG C, 200 DEG C, 220 DEG C, and Figure 10 (a), (b), the left figure of (c) represent different putting respectively from right figure The Electronic Speculum figure of big multiple, left figure is 20000 times, and right figure is 10000 times；
Figure 11 is Al in embodiment 32O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The XRD figure spectrum of the SAPO-18 molecular sieve crystal Cl) synthesized；
Figure 12 is Al in embodiment 42O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 10mol% NH4The stereoscan photograph of the SAPO-18 molecular sieve crystal Cl) synthesized, wherein in Figure 12 shown in (a), (b), (c), (d), (e) Molecular sieve crystal synthesis time ammonium chloride addition be respectively 0.1mol%, 1mol%, 2mol%, 4mol%, 10mol% (it is converted into Al with source of aluminium2O3Molal quantity on the basis of count), Figure 12 (a), (b), (c), (d), the left figure of (e) divide with right figure Not representing the Electronic Speculum figure of different amplification, left figure is 50000 times, and right figure is 20000 times；
Figure 13 is Al in embodiment 42O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 8mol% NH4The XRD figure spectrum of the SAPO-18 molecular sieve crystal Cl) synthesized；
Figure 14 is Al in embodiment 52O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% Additive) stereoscan photograph of SAPO-18 molecular sieve crystal that synthesizes, wherein (a), (b) in Figure 14, (c), (d), (e), When the molecular sieve crystal shown in () synthesizes f, additive is respectively 1-butyl-3 methy limidazolium salt, ammonium chloride, biphosphate Ammonium, ammonium fluoride, ammonia, di-n-propylamine, Figure 14 (a), (b), (c), (d), (e), the left figure of (f) represent different from right figure respectively The Electronic Speculum figure of amplification, left figure is 50000 times, and right figure is 20000 times；
Figure 15 is Al in embodiment 52O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% Additive) synthesize SAPO-18 molecular sieve crystal XRD figure spectrum, consistent with standard diagram；
Figure 16 is Al in embodiment 52O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% Additive) nitrogen adsorption isotherm of SAPO-18 molecular sieve crystal that synthesizes；
Figure 17 is Al in embodiment 62O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The stereoscan photograph of SAPO-18 and the SAPO-34 molecular sieve crystal Cl) synthesized, wherein (a), (b) in Figure 17, (c), The aluminum source added when the molecular sieve crystal shown in (), (e), (f) synthesizes d and silicon source are respectively aluminum isopropylate. and Ludox, isopropyl Aluminium alcoholates and tetraethyl orthosilicate, aluminium hydroxide and Ludox, aluminium hydroxide and tetraethyl orthosilicate, aluminum isopropylate. are molten with silicon gas Glue, aluminium hydroxide and silicon aerosol, Figure 17 (a), (b), (c), (d), (e), (f) left figure represent different amplification respectively from right figure The Electronic Speculum figure of multiple, left figure is 50000 times, and right figure is 20000 times；
Figure 18 is Al in embodiment 62O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4The XRD figure spectrum of SAPO-18 and the SAPO-34 molecular sieve crystal Cl) synthesized；
Figure 19 is Al in embodiment 22O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4Methanol conversion rate curve in time in the methanol to olefins reaction (MTO) of the SAPO-18 molecular sieve crystal Cl) synthesized；
Figure 20 is Al in embodiment 22O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3 (1wt% crystal seed, 4mol% NH4Products distribution curve in the methanol to olefins reaction (MTO) of the SAPO-18 molecular sieve crystal Cl) synthesized.
Detailed description of the invention
Before further describing the specific embodiment of the invention, it should be appreciated that protection scope of the present invention is not limited to down State specific specific embodiments；It is also understood that the term used in the embodiment of the present invention is specific concrete in order to describe Embodiment rather than in order to limit the scope of the invention.The test method of unreceipted actual conditions in the following example, Generally according to normal condition, or according to the condition proposed by each manufacturer.
Embodiment 1
Al in the present embodiment2O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3, prepares SAPO-34 molecular sieve, adds 1wt% crystal seed is (with Al2O3Addition for calculate benchmark), investigate the response time impact.Specifically include following steps:
1) 10.212 grams of aluminum isopropylate., 5.763 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 14.123 grams of water are mixed Stir 3 hours after conjunction, add 1.125 grams of Ludox (mass fraction is 40% aqueous solution), stir 1 hour, add 10.519 grams Tetraethyl ammonium hydroxide solution (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.025 gram of SAPO- 34 molecular sieve crystal seed aged at room temperature 24 hours；
2) by step 1) molecular sieve synthesis mother liquid prepared pours in evaporating dish, dries 24 hours at 80 DEG C, after drying Mother solution grind into powder；
3) powder is divided into five parts put in corresponding numbering stainless steel reaction pipe, is separately added into the deionization of 0.27 gram Water, reacts the corresponding time in 220 DEG C of oil baths respectively, washs, dries and prepare SAPO-34 molecular sieve crystal.
Fig. 1 is the stereoscan photograph of the SAPO-34 molecular sieve of the method synthesis, wherein figure molecule shown in (a), (b) The sieve Opacity in lens time is respectively 6 hours, 9 hours, and Fig. 1 (a), left figure and the right figure of (b) represent different amplification respectively Electronic Speculum figure, left figure is 20000 times, and right figure is 10000 times.Being found out by figure, SAPO-34 zeolite crystal is rendered as flake, Size is uniform, and size is at 300 ran.
Fig. 2 is the XRD figure spectrum of the SAPO-34 molecular sieve of the method synthesis, consistent with standard diagram.
Fig. 3 is the nitrogen adsorption isotherm of the SAPO-34 molecular sieve crystal obtained in the present embodiment.Generated time is 9 little Time sample BET specific surface area be 535m2/ g, wherein the specific surface area of micropore is 484m2/ g, Micropore volume is 0.19cm3/g。
Embodiment 2
Al2O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3, prepares SAPO-18 and SAPO-34 molecular sieve, adds 1wt% crystal seed is (with Al2O3Addition for calculate benchmark), 4mol%NH4Cl is (with Al2O3Addition for calculate benchmark), examine Examine the impact in response time.Specifically include following steps:
1) 10.212 grams of aluminum isopropylate., 5.763 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 14.123 grams of water are mixed Stir 3 hours after conjunction, add 1.125 grams of Ludox (mass fraction is 40% aqueous solution), stir 1 hour, add 10.519 grams Tetraethyl ammonium hydroxide solution (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.025 gram of SAPO- 34 molecular sieve crystal seed aged at room temperature 24 hours；
2) by step 1) molecular sieve synthesis mother liquid prepared pours in evaporating dish, dries 24 hours at 80 DEG C, after drying Mother solution in add 0.054 gram of NH4Cl, grind into powder after the two mix homogeneously；
3) powder is divided into eight parts put in corresponding numbering stainless steel reaction pipe, is separately added into the deionization of 0.169 gram Water, reacts the corresponding time in 220 DEG C of oil baths respectively, washs, dries and prepare SAPO-18 and SAPO-34 molecular sieve crystal.
Fig. 4 is the stereoscan photograph of SAPO-18 and SAPO-34 molecular sieve of the method synthesis, wherein figure (a), (b), Molecular sieve crystal generated time shown in (c), (d), (e), (f), (g), (h) be respectively 10 minutes, 20 minutes, 40 minutes, 60 Minute, 120 minutes, 240 minutes, 360 minutes, 480 minutes, wherein the left figure of Fig. 4 (a) and right figure amplification are respectively 20000 times and 10000 times, Fig. 4 (b), (c), (d), (e), (f), (g), the left figure of (h) are respectively with right figure amplification 50000 times and 20000 times.Found out by figure, and do not add NH4The synthetic system of Cl is compared, the SAPO-prepared under the method 18 and SAPO-34 zeolite crystal well-crystallizeds, are rendered as flake, and size is uniform, and size is at 300 ran.
Fig. 5 is the XRD figure spectrum of SAPO-18 and the SAPO-34 molecular sieve of the method synthesis, consistent with standard diagram.
Fig. 6 is the nitrogen adsorption isotherm of SAPO-18 and the SAPO-34 molecular sieve crystal obtained in the present embodiment.Synthesis Time be 1 hour obtain SAPO-18 sample BET specific surface area be 741m2/ g, wherein the specific surface area of micropore is 684m2/ g, Micropore volume is 0.27cm3/g.Generated time be the BET specific surface area of SAPO-34 sample obtained for 2 hours be 675m2/ g, its The specific surface area of middle micropore is 660m2/ g, Micropore volume is 0.26cm3/g。
Fig. 7 is the Si element nuclear-magnetism curve of SAPO-18 and the SAPO-34 molecular sieve of the method synthesis.
Fig. 8 is the Al element nuclear-magnetism curve of SAPO-18 and the SAPO-34 molecular sieve of the method synthesis.
Fig. 9 is the P element nuclear-magnetism curve of SAPO-18 and the SAPO-34 molecular sieve of the method synthesis.
Embodiment 3
Al2O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3, prepares SAPO-18 molecular sieve, adds 1wt% crystal seed (with Al2O3Addition for calculate benchmark), 4mol%NH4Cl is (with Al2O3Addition for calculate benchmark), investigate synthesis temperature Impact.Specifically include following steps:
1) 10.212 grams of aluminum isopropylate., 5.763 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 14.123 grams of water are mixed Stir 3 hours after conjunction, add 1.125 grams of Ludox (mass fraction is 40% aqueous solution), stir 1 hour, add 10.519 grams Tetraethyl ammonium hydroxide solution (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.025 gram of SAPO- 34 molecular sieve crystal seed aged at room temperature 24 hours；
2) by step 1) molecular sieve synthesis mother liquid prepared pours in evaporating dish, dries 24 hours at 80 DEG C, after drying Mother solution in add 0.054 gram of NH4Cl, grind into powder after the two mix homogeneously；
3) powder is divided into three parts put in corresponding numbering stainless steel reaction pipe, is separately added into the deionization of 0.45 gram Water, react 1 hour respectively at 180 DEG C, 200 DEG C, 220 DEG C, wash, dry and prepare SAPO-18 molecular sieve crystal.
Figure 10 is the stereoscan photograph of SAPO-18 and SAPO-34 molecular sieve of the method synthesis, wherein figure (a), (b), C the molecular sieve crystal synthesis temperature shown in () is respectively 180 DEG C, 200 DEG C, 220 DEG C, Figure 10 (a), (b), left figure and the right side of (c) Figure represents the Electronic Speculum figure of different amplification respectively, and left figure is 20000 times, and right figure is 10000 times.Found out by figure, SAPO-18 With SAPO-34 zeolite crystal well-crystallized, being rendered as flake, size is uniform, and size is at 300 ran.
Figure 11 is the XRD figure spectrum of the SAPO-18 molecular sieve of the method synthesis, consistent with standard diagram.
Embodiment 4
Al2O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3, prepares SAPO-18 molecular sieve, adds 1wt% crystal seed (with Al2O3Addition for calculate benchmark), investigate NH4Cl addition is (with Al2O3Addition be calculate benchmark) impact.Tool Body comprises the following steps:
1) 10.212 grams of aluminum isopropylate., 5.763 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 14.123 grams of water are mixed Stir 3 hours after conjunction, add 1.125 grams of Ludox (mass fraction is 40% aqueous solution), stir 1 hour, add 10.519 grams Tetraethyl ammonium hydroxide solution (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.025 gram of SAPO- 34 molecular sieve crystal seed aged at room temperature 24 hours；
2) by step 1) molecular sieve synthesis mother liquid prepared pours in evaporating dish, dries 24 hours at 80 DEG C, after drying Mother solution grind into powder；
3) powder is divided into seven parts put in corresponding numbering stainless steel reaction pipe, is separately added into the deionization of 0.193 gram Water and the NH of corresponding amount4Cl reacts 1 hour in 220 DEG C, washs, dries and prepare SAPO-18 molecular sieve crystal.
Figure 12 is the stereoscan photograph of SAPO-18 molecular sieve of the method synthesis, wherein figure (a), (b), (c), (d), Shown in (e) molecular sieve crystal synthesis time ammonium chloride addition be respectively 0.1mol%, 1mol%, 2mol%, 4mol%, 10mol% (is converted into Al with source of aluminium2O3Molal quantity on the basis of count), Figure 12 (a), (b), (c), (d), (e) left figure with Right figure represents the Electronic Speculum figure of different amplification respectively, and left figure is 50000 times, and right figure is 20000 times.Found out by figure, add A small amount of NH4Cl can promote that SAPO-18 zeolite crystal crystallizes, and product well-crystallized, is rendered as flake, and size is uniform, Size is at 300 ran.
Figure 13 is the XRD figure spectrum of the SAPO-18 molecular sieve of the method synthesis, consistent with standard diagram.
Embodiment 5
Al2O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3, prepares SAPO-18 molecular sieve, adds 1wt% crystal seed (with Al2O3Addition for calculate benchmark), investigate 4mol% different additive (with Al2O3Addition for calculate benchmark) Impact.Specifically include following steps:
1) 10.212 grams of aluminum isopropylate., 5.763 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 14.123 grams of water are mixed Stir 3 hours after conjunction, add 1.125 grams of Ludox (mass fraction is 40% aqueous solution), stir 1 hour, add 10.519 grams Tetraethyl ammonium hydroxide solution (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.025 gram of SAPO- 34 molecular sieve crystal seed aged at room temperature 24 hours；
2) by step 1) molecular sieve synthesis mother liquid prepared pours in evaporating dish, dries 24 hours at 80 DEG C, after drying Mother solution grind into powder；
3) powder is divided into six parts put in corresponding numbering stainless steel reaction pipe, is separately added into the deionization of 0.225 gram The additive of water and corresponding amount reacts 1 hour in 220 DEG C, washs, dries and prepare SAPO-18 molecular sieve crystal.
Figure 14 is the stereoscan photograph of SAPO-18 molecular sieve of the method synthesis, wherein figure (a), (b), (c), (d), When the molecular sieve crystal shown in (), (f) synthesizes e, additive is respectively 1-butyl-3 methy limidazolium salt, ammonium chloride, di(2-ethylhexyl)phosphate Hydrogen ammonium, ammonium fluoride, ammonia, di-n-propylamine, Figure 14 (a), (b), (c), (d), (e), left figure and the right figure of (f) represent not respectively With the Electronic Speculum figure of amplification, left figure is 50000 times, and right figure is 20000 times.Found out by figure, add a small amount of NH4Cl can promote SAPO-18 zeolite crystal crystallizes, and product well-crystallized, is rendered as flake, and size is uniform, and size is at 300 ran.
Figure 15 is the XRD figure spectrum of the SAPO-18 molecular sieve of the method synthesis, consistent with standard diagram.
Figure 16 is the nitrogen adsorption isotherm of the SAPO-18 molecular sieve crystal obtained in the present embodiment.Add 4mol% NH4F gained sample BET specific surface area is 517m2/ g, wherein the specific surface area of micropore is 439m2/ g, Micropore volume is 0.17cm3/g。
Embodiment 6
Al2O3:SiO2:P2O5:TEAOH:H2O=1:0.3:1:1:3, prepares SAPO-18 molecular sieve, adds 1wt% crystal seed (with Al2O3Addition for calculate benchmark), 4mol%NH4Cl is (with Al2O3Addition for calculating benchmark), investigate different silicon Source, the impact in aluminum source.Specifically include following steps:
1) by after 1.89 grams of aluminum isopropylate., 1.07 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 10.95 grams of water mixing Stir 3 hours, add 0.21 gram of Ludox (mass fraction is 40% aqueous solution), stir 1 hour, add 1.94 grams of tetraethyl hydrogen Ammonium hydroxide solution (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.005 gram of SAPO-34 molecular sieve Crystal seed aged at room temperature 24 hours；Or
Stir after 1.89 grams of aluminum isopropylate., 1.07 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 10.95 grams of water mixing Mix 3 hours, add 0.29 gram of tetraethyl orthosilicate, stir 1 hour, add 1.94 grams of tetraethyl ammonium hydroxide solution (TEAOH, Mass fraction is 35% aqueous solution), stir 1 hour, be eventually adding 0.005 gram of SAPO-34 molecular sieve crystal seed aged at room temperature 24 Hour；Or
By 0.89 gram of aluminium hydroxide (quality of alumina mark is 53%), 1.07 grams of phosphoric acid, (mass fraction is 85% water-soluble Liquid) and the mixing of 10.95 grams of water after stir 3 hours, adds 0.21 gram of Ludox (mass fraction is 40% aqueous solution), stirs 1 little Time, add 1.94 grams of tetraethyl ammonium hydroxide solution (TEAOH, mass fraction is 35% aqueous solution), stir 1 hour, finally add Enter 0.005 gram of SAPO-34 molecular sieve crystal seed aged at room temperature 24 hours；Or
By 0.89 gram of aluminium hydroxide (quality of alumina mark is 53%), 1.07 grams of phosphoric acid, (mass fraction is 85% water-soluble Liquid) and the mixing of 10.95 grams of water after stir 3 hours, add 0.29 gram of tetraethyl orthosilicate, stir 1 hour, add 1.94 grams of tetrems Base Ammonia (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.005 gram of SAPO-34 and divides Son sieve crystal seed aged at room temperature 24 hours；Or
Stir after 1.89 grams of aluminum isopropylate., 1.07 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 10.95 grams of water mixing Mix 3 hours, add 0.083 gram of silicon aerosol, stir 1 hour, add 1.94 grams of tetraethyl ammonium hydroxide solution (TEAOH, quality Mark is 35% aqueous solution), stir 1 hour, be eventually adding 0.005 gram of SAPO-34 molecular sieve crystal seed aged at room temperature 24 hours； Or
By 0.89 gram of aluminium hydroxide (quality of alumina mark is 53%), 1.07 grams of phosphoric acid, (mass fraction is 85% water-soluble Liquid) and the mixing of 10.95 grams of water after stir 3 hours, add 0.083 gram of silicon aerosol, stir 1 hour, add 1.94 grams of tetraethyls Ammonia (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.005 gram of SAPO-34 molecule Sieve crystal seed aged at room temperature 24 hours；
2) molecular sieve synthesis mother liquid step prepared is poured in evaporating dish respectively, dries 24 hours at 80 DEG C, will dry After mother solution grind into powder；
3) by step 2) grind in the stainless steel reaction pipe that the powder obtained is respectively put into corresponding numbering, it is separately added into 0.25 Gram deionized water and 0.01 gram of NH4Cl reacts 1 hour in 220 DEG C, washs, dries and prepare SAPO-18 and SAPO-34 Molecular sieve crystal.
Figure 17 is the stereoscan photograph of SAPO-18 and SAPO-34 molecular sieve of the method synthesis, wherein figure (a), (b), Aluminum source and the silicon source added during molecular sieve crystal synthesis shown in (c), (d), (e), (f) be respectively aluminum isopropylate. and Ludox, Aluminum isopropylate. and tetraethyl orthosilicate, aluminium hydroxide and Ludox, aluminium hydroxide and tetraethyl orthosilicate, aluminum isopropylate. and silicon gas Colloidal sol, aluminium hydroxide and silicon aerosol, Figure 17 (a), (b), (c), (d), (e), (f) left figure represent different putting respectively from right figure The Electronic Speculum figure of big multiple, left figure is 50000 times, and right figure is 20000 times.Found out by figure, SAPO-18 and SAPO-prepared 34 zeolite crystal well-crystallizeds, are rendered as flake, and size is uniform, and size is at 300 ran.
Figure 18 is the XRD figure spectrum of SAPO-18 and the SAPO-34 molecular sieve of the method synthesis, consistent with standard diagram.
Embodiment 7
Al2O3:SiO2:P2O5:TEAOH:H2O=1:0.05:0.5:5:10, prepares SAPO-18 molecular sieve, adds 0.1wt% crystal seed is (with Al2O3Addition for calculate benchmark), investigate 4mol% different additive (with Al2O3Addition be Calculate benchmark) impact.Specifically include following steps:
1) 10.212 grams of aluminum isopropylate., 2.882 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 14.123 grams of water are mixed Stir 3 hours after conjunction, add 0.188 gram of Ludox (mass fraction is 40% aqueous solution), stir 1 hour, add 52.595 grams Tetraethyl ammonium hydroxide solution (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.003 gram of SAPO- 34 molecular sieve crystal seed aged at room temperature 24 hours；
2) by step 1) molecular sieve synthesis mother liquid prepared pours in evaporating dish, dries 24 hours at 80 DEG C, after drying Mother solution grind into powder；
3) powder is divided into six parts put in corresponding numbering stainless steel reaction pipe, is separately added into the deionized water of 0.75 gram And the additive of corresponding amount reacts 1 hour in 220 DEG C, wash, dry and prepare SAPO-18 molecular sieve crystal.
Embodiment 8
Al2O3:SiO2:P2O5:TEAOH:H2O=1:0.8:3:0.1:1, prepares SAPO-18 molecular sieve, adds 5wt% brilliant Plant (with Al2O3Addition for calculate benchmark), investigate 4mol% different additive (with Al2O3Addition for calculate benchmark) Impact.Specifically include following steps:
1) 10.212 grams of aluminum isopropylate., 17.289 grams of phosphoric acid (mass fraction is 85% aqueous solution) and 14.123 grams of water are mixed Stir 3 hours after conjunction, add 3 grams of Ludox (mass fraction is 40% aqueous solution), stir 1 hour, add 1.052 grams of tetraethyls Ammonia (TEAOH, mass fraction is 35% aqueous solution), stirs 1 hour, is eventually adding 0.125 gram of SAPO-34 molecule Sieve crystal seed aged at room temperature 24 hours；
2) by step 1) molecular sieve synthesis mother liquid prepared pours in evaporating dish, dries 24 hours at 80 DEG C, after drying Mother solution grind into powder；
3) powder is divided into six parts put in corresponding numbering stainless steel reaction pipe, is separately added into the deionization of 0.075 gram The additive of water and corresponding amount reacts 1 hour in 220 DEG C, washs, dries and prepare SAPO-18 molecular sieve crystal.
When embodiment provides numerical range, it should be appreciated that unless the present invention is otherwise noted, two ends of each numerical range Between point and two end points, any one numerical value all can be selected for.Unless otherwise defined, in the present invention use all technology and The same meaning that scientific terminology and those skilled in the art of the present technique are generally understood that.Except in embodiment use concrete grammar, equipment, Outside material, according to those skilled in the art's grasp to prior art and the record of the present invention, it is also possible to use and this Any method, equipment and the material of the prior art that the method described in inventive embodiments, equipment, material are similar or equivalent comes real The existing present invention.

Claims (15)

1. the solvent-free method preparing SAPO-18 or SAPO-34 molecular sieve, comprises the steps:
1) silicon source, aluminum source, water, phosphoric acid, template and SAPO-34 molecular sieve crystal seed are mixed to get molecular sieve mother solution；
2) by step 1) molecular sieve mother solution dry, and grind into powder；
3) described powder mixes with water, and adds additive；
4) crystallization synthesis SAPO-18 or SAPO-34 molecular sieve.
Method the most according to claim 1, it is characterised in that: step 1) described in template be tetraethyl ammonium hydroxide.
Method the most according to claim 1, it is characterised in that: step 1) in, silicon source is converted into SiO2, aluminum source is converted into Al2O3, phosphoric acid is converted into P2O5Meter, SiO2、Al2O3、P2O5, template and H2The mol ratio of O is 0.05～0.8:1:0.5～3: 0.1～5:10～100.
Method the most according to claim 1, it is characterised in that: it is converted into Al with source of aluminium2O3Quality on the basis of count, step Rapid 1) addition of SAPO-34 molecular sieve crystal seed described in is 0.1～5wt%.
Method the most according to claim 1, it is characterised in that: step 1) in, described silicon source is Ludox, silicon aerosol and just One or more in tetraethyl orthosilicate.
Method the most according to claim 1, it is characterised in that: step 1) in, source of aluminium is aluminium hydroxide and aluminum isopropylate. In one or both.
Method the most according to claim 1, it is characterised in that: step 1) in, use stirring mixing during the mixing of molecular sieve mother solution, Mixing time is 1 hour～3 days.
Method the most according to claim 1, it is characterised in that: step 2) in dry temperature in baking step be 80～85 DEG C.
Method the most according to claim 1, it is characterised in that: step 3) described in additive be ammonium chloride, di-n-propylamine, fluorine Change one or more in ammonium, ammonia, ammonium dihydrogen phosphate, 1-butyl-3-methy limidazolium salt.
Method the most according to claim 1, it is characterised in that: it is converted into Al with source of aluminium2O3Molal quantity on the basis of count, Step 3) described in the addition of additive be 0.1～10mol%.
11. methods according to claim 1, it is characterised in that: it is converted into Al with source of aluminium2O3Molal quantity on the basis of count, Step 3) described in the addition of water be described Al2O31～10 times of molal quantity.
12. methods according to claim 1, it is characterised in that: step 1) in time to select aluminum isopropylate. be aluminum source, crystallization synthesizes Time is constantly synthesis SAPO-18 molecular sieve little less than 1, crystallization generated time constantly synthesis SAPO-34 molecule little more than 1 Sieve；Step 1) in select aluminium hydroxide when being aluminum source, crystallization generated time be constantly synthesis SAPO-18 molecular sieve little less than 1, crystalline substance It is combined to time constantly synthesis SAPO-34 molecular sieve little not less than 1.
13. method according to claim 1, it is characterised in that: step 4) in synthesis mode be static monitor.
14. methods according to claim 1, it is characterised in that: step 4) in synthesis temperature be 160～220 DEG C.
15. methods according to claim 1, it is characterised in that: step 4) in generated time be 10 minutes～24 hours.
CN201610614191.XA 2016-07-29 2016-07-29 The solvent-free method preparing SAPO 18 or SAPO 34 molecular sieve Pending CN106185983A (en)

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CN107382331A (en) * 2017-06-28 2017-11-24 常州莱尚纺织品有限公司 A kind of anti-slag type tundish paint
CN110270368A (en) * 2018-03-14 2019-09-24 北京化工大学 A method of no solwution method synthesis is used for the embedded catalyst material of C-1 chemistry
CN111032571A (en) * 2017-08-14 2020-04-17 全南大学校产学协力团 Process for the manufacture of zeolites with controlled aluminium content by adjusting the composition of the synthesis mother liquor

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CN103121698A (en) * 2013-02-01 2013-05-29 浙江大学 Method for synthesizing SAPO (silicoaluminophosphate)-34 by solid-phase grinding
CN104340993A (en) * 2013-08-06 2015-02-11 中国科学院上海高等研究院 Preparation method of SAPO-34 molecular sieve membrane
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Publication number Priority date Publication date Assignee Title
CN107324353A (en) * 2017-06-26 2017-11-07 神华集团有限责任公司 The preparation method of the molecular sieves of SAPO 34 and the preparation method of catalyst
CN107382331A (en) * 2017-06-28 2017-11-24 常州莱尚纺织品有限公司 A kind of anti-slag type tundish paint
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CN111032571B (en) * 2017-08-14 2023-06-30 全南大学校产学协力团 Method for producing zeolite with controlled aluminium content by adjusting composition of synthesis mixture
CN110270368A (en) * 2018-03-14 2019-09-24 北京化工大学 A method of no solwution method synthesis is used for the embedded catalyst material of C-1 chemistry
CN110270368B (en) * 2018-03-14 2020-09-04 北京化工大学 Method for synthesizing carbon-chemical embedded catalyst material by solution-free method

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Application publication date: 20161207