CN107915237B - A kind of twin SAPO-34 molecular sieve and its synthetic method and a kind of method of methanol-to-olefins - Google Patents

A kind of twin SAPO-34 molecular sieve and its synthetic method and a kind of method of methanol-to-olefins Download PDF

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CN107915237B
CN107915237B CN201610887406.5A CN201610887406A CN107915237B CN 107915237 B CN107915237 B CN 107915237B CN 201610887406 A CN201610887406 A CN 201610887406A CN 107915237 B CN107915237 B CN 107915237B
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molecular sieve
crystallization
sapo
phosphorus
twin
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CN107915237A (en
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梁世航
张羿
王永睿
慕旭宏
徐广通
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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China Petrochemical Corp
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
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    • 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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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C—CHEMISTRY; METALLURGY
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The present invention relates to catalysis materials to synthesize field, disclose a kind of twin SAPO-34 molecular sieve and its synthetic method, including synthesizing the twin SAPO-34 molecular sieve using hydro-thermal method, hydrothermal crystallizing will be carried out containing the mixed liquor of phosphorus source, silicon source, silicon source, template and water, is then separated by solid-liquid separation, is dry；And including synthesizing twin SAPO-34 molecular sieve using phosphorus aluminium dry glue liquid phase conversion, aging will be carried out containing the mixed liquor A of phosphorus source, silicon source and water, then it dries, phosphorus aluminium dry glue is made, and hydrothermal crystallizing will be carried out containing the raw mixture B of phosphorus aluminium dry glue, silicon source, template and water, then it is separated by solid-liquid separation, is dry, the template is pyrrolidines.It is the cube that a triangular pyramid is all had at the center of six faces that the present invention, which synthesizes twin SAPO-34 molecular sieve crystal pattern,.Twin SAPO-34 molecular sieve synthesized by the present invention can be used for converting oxygen-containing compound to low-carbon olefins reaction, especially in methanol-to-olefins reaction reaction, the selectivity of light olefin with preferable ethylene and propylene.

Description

A kind of twin SAPO-34 molecular sieve and its synthetic method and a kind of methanol-to-olefins Method
Technical field
The present invention relates to a kind of SAPO-34 molecular sieve and its synthetic method, and the invention further relates to a kind of sides of methanol-to-olefins Method.
Background technique
SAPO-34 molecular sieve is U.S. combinating carbide company in a kind of novel aluminium silicophosphate molecular sieve of exploitation in 1984. Since SAPO-34 molecular sieve has suitable pore size, cellular structure, acid strength and good thermal stability, hydro-thermal steady The advantages that qualitative, makes it show good application feature in gas absorption separation, all kinds of hydrocarbon conversion catalyst fields, especially exists There is very high selectivity to ethylene, propylene in methanol-to-olefins reaction (MTO), shows excellent catalytic performance, mesh Before have become the preferred catalyst of MTO technical process.
The topological structure of SAPO-34 molecular sieve is Chabazite-type (CHA), and space group R-3m belongs to trigonal system, structure cell ginseng Numberα=94.47 °, β=94.47 °, γ=94.47 ° have and are pressed by double hexatomic rings Octatomic ring elliposoidal cage (CHA cage) and three dimensional intersection cellular structure made of being accumulated according to ABC mode, pore size be 0.38nm × 0.38nm, cage size are 1.0nm × 0.67nm × 0.67nm, belong to small pore molecular sieve.
The typical crystal morphology of SAPO-34 molecular sieve be cube pattern, this CN103663490A, In numerous patents such as CN103818928A, CN103896305A, CN102336413A, CN104418358A, CN102464338A All have been reported that.In recent years, researcher both domestic and external has done a large amount of research to SAPO-34 molecular sieve, and there are many different It is synthesized in the SAPO-34 molecular sieve of normal cubic pattern, such as sheet-like morphology, spherical morphology.
For example, CN103011188A has opened a kind of synthetic method with SAPO-34 molecular sieve, this method will contain aluminium Source, silicon source, phosphorus source, organic amine template and water mixed solution be placed in autoclave, by the way of microwave heating, lead to Control microwave synthesis condition is crossed, the SAPO-34 molecular sieve of nanometer spherical and sheet-like morphology has been synthesized.Wherein, the organic formwork Agent is the mixture of one or more of diethylamine, triethylamine, tetraethyl ammonium hydroxide, morpholine, dipropylamine.
For another example, CN104986780A discloses a kind of synthetic method of SAPO-34 molecular sieve, and this method uses hydrothermal synthesis Method, using is to be and the second template cetyl trimethylammonium bromide, cetyl front three by the first template triethylamine The composite mould plate agent of base ammonium hydroxide or hexadecyltrimethylammonium chloride composition is 180-200 DEG C, when crystallization in crystallization temperature Between to have synthesized the SAPO-34 molecular sieve of nanoscale twins crystal morphology under conditions of 10-50h.
For another example, CN103936027A discloses a kind of method of SAPO-34 molecular sieve, and this method is added in crystallization process Biomass suspension is 180-200 DEG C in crystallization temperature, under conditions of crystallization time is 24-72h, has synthesized flower-like microsphere shape The SAPO-34 molecular sieve of looks.Used template is triethylamine, diethylamine or tetraethyl ammonium hydroxide.
It is normal life though above-mentioned SAPO-34 molecular sieve causes pattern different because of synthesis condition and template change due to Long SAPO-34 molecular sieve crystal.In addition, there is also it is a kind of because molecular sieve itself crystal growth generate defect due to formed it is twin It is brilliant.From crystallography, twin refers to two crystal (or two parts of a crystal) along a public crystal face (i.e. specific orientation Relationship) mirror-symmetrical orientation relationship is constituted, the two crystal are known as " twin ".
About molecular sieve twin growth phenomenon and reason document (Mineralogical Magazine, 2000,64 (1): It is reported in 1-8.).The document describes A type molecular sieve tool, and there are two the SEM patterns that independent cubic grain interpenetrates.From From the point of view of pattern, the twin of A type molecular sieve is to rotate 180 ° around triad by an individual cubic grain to be formed.From structure From the point of view of, the formation of A type molecular sieve twin be on the one of face of crystal recurring structure failure and generate.The twin structure of formation Two sodalite cages of A type molecular sieve may be made to connect together by hexatomic ring, 3 D pore canal is caused to stress in twin plane two New arrangement.Therefore, the appearance of molecular sieve twin changes its structure and pattern, to will lead to the materialization of molecular sieve Matter is different from routine.
Document (Crystal Growth&Design, 2010,10 (7): 2824-2828.) is reported is in crystallization temperature 200 DEG C, under conditions of crystallization time is 48h, use hydrofluoric acid (HF) for mineralizer, morpholine is that template synthesizes SAPO-34 points When son sieve, crystal morphology is that some small twin growth objects outstanding are grown on the Sharp edge of normal cubic crystal grain.
Summary of the invention
It is an object of the invention on the basis of existing technology, provide a kind of tool, there are six all have one at the center of face The twin SAPO-34 molecular sieve and its synthetic method of the cube pattern of triangular pyramid and application.The molecular sieve can be used for oxygen-containing Compound converts reaction for preparing light olefins, especially in methanol-to-olefins reaction reaction, has preferable ethylene and third The selectivity of light olefin of alkene.
Therefore, according to the first aspect of the invention, the present invention provides a kind of twin SAPO-34 molecular sieves, wherein institute The crystal morphology for stating twin SAPO-34 molecular sieve is the cube that a triangular pyramid is all had at the center of six faces.
According to the second aspect of the invention, the present invention also provides a kind of synthesis of twin SAPO-34 molecular sieve Method, wherein the synthetic method includes:
(1) a kind of mixed liquor is provided, the mixed liquor contains phosphorus source, silicon source, silicon source, template and water, phosphorus source with P2O5Meter, source of aluminium is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus source, silicon source, silicon source, the molar ratio of template and water are 0.6-1.2:0.05-1.2:1:1.5-10:3-100, preferably 0.8-1.2:0.1-1:1:1.5-5:5-50；
(2) mixed liquor is subjected to hydrothermal crystallizing；
(3) mixture for obtaining hydrothermal crystallizing is separated by solid-liquid separation, and obtained solid phase is dried and optionally Roasting；
Wherein, the template is pyrrolidines, N- crassitude, 2- crassitude, 3- crassitude and 2,5- At least one of dimethyl pyrrolidine.
According to the third aspect of the present invention, the present invention also provides the conjunctions of another twin SAPO-34 molecular sieve At method, wherein the synthetic method includes:
(1) mixed liquor A is provided, the mixed liquor A contains phosphorus source, silicon source and water, and phosphorus source is with P2O5Meter, source of aluminium With Al2O3Meter, the molar ratio of phosphorus source, silicon source and water are 0.6-1.2:1:20-70, preferably 0.8-1.2:1:20-60；
(2) mixed liquor A is subjected to aging, then dried, phosphorus aluminium dry glue is made；
(3) raw mixture B is provided, the raw mixture B contains phosphorus aluminium dry glue, silicon source, template made from step (2) Agent and water, the phosphorus aluminium dry glue is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus aluminium dry glue, silicon source, the molar ratio of template and water Are as follows: 1:0.05-1.2:1.5-10:3-100, preferably 1:0.1-1:1.5-5:5-50；
(4) raw mixture B is subjected to hydrothermal crystallizing；
(5) mixture for obtaining hydrothermal crystallizing is separated by solid-liquid separation, and obtained solid phase is dried and optionally Roasting；
Wherein, the template is pyrrolidines, N- crassitude, 2- crassitude, 3- crassitude and 2,5- At least one of dimethyl pyrrolidine.
The present invention has synthesized the pure phase twin SAPO- with regular morphology as template using pyrrolidines for the first time 34 molecular sieves.Had using the SAPO-34 molecular sieve that hydrothermal synthesis method or phosphorus aluminium dry glue liquid phase conversion synthesize regular twin Brilliant crystal morphology, twin pattern are the cube that a triangular pyramid is all had at six faces center of normal cubic crystal grain. It is different from traditional SAPO- in cellular structure using the twin SAPO-34 molecular sieve that pyrrolidines are prepared as template 34 molecular sieves, there are octatomic ring ducts to intersect connection phenomenon, allows to react for converting oxygen-containing compound to low-carbon olefins, Excellent catalytic performance especially is shown in MTO catalysis reaction, there is preferable ethylene (C2Alkene) and propylene (C3Alkene) Selectivity of light olefin.
In addition, the templates such as common triethylamine, tetraethyl ammonium hydroxide exist in SAPO-34 molecular sieve industrial production It is heated to decompose in the synthesis process of SAPO-34, it cannot be recycled, cause production cost high, and can not realize The clean manufacturing that template is recycled pollutes environment.Pyrrolidines template stable structure of the present invention, It in sieve synthesis procedure, does not decompose, the industrial clean manufacturing of template recycling may be implemented, advantageously reduce Production cost, and reduce environmental pollution.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the XRD spectra for the sieve sample that embodiment 1 synthesizes；
Fig. 2 is the SEM photograph for the sieve sample that embodiment 1 synthesizes；
The liquid that Fig. 3 is 3 template used doses of embodiment13C MAS NMR spectra；
Fig. 4 is the liquid of 3 molecular sieve synthesis mother liquid of embodiment13C MAS NMR spectra；
Fig. 5 is the XRD spectra for the sieve sample that embodiment 8 synthesizes；
Fig. 6 is the SEM photograph for the sieve sample that embodiment 8 synthesizes；
Fig. 7 is the XRD spectra for the sieve sample that embodiment 10 synthesizes；
Fig. 8 is the SEM photograph for the sieve sample that embodiment 10 synthesizes；
Fig. 9 is the XRD spectra for the sieve sample that embodiment 14 synthesizes；
Figure 10 is the SEM photograph for the sieve sample that embodiment 14 synthesizes；
Figure 11 is the XRD spectra for the sieve sample that embodiment 15 synthesizes；
Figure 12 is the SEM photograph for the sieve sample that embodiment 15 synthesizes；
Figure 13 is the SEM photograph for the sieve sample that comparative example 1 synthesizes；
Figure 14 is the XRD spectra for the sieve sample that comparative example 2 synthesizes；
Figure 15 is the SEM photograph for the sieve sample that comparative example 2 synthesizes.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
Technical term in the present invention provides defining from it for definition, does not provide then usually the containing by this field of definition Reason and good sense solution.
Template in the present invention, in the art also referred to as structure directing agent or Organic structure directing agent.
According to the first aspect of the invention, the SAPO-34 molecular sieve provided by the invention is pure phase twin SAPO-34 Molecular sieve has regular twin crystal morphology, and crystallinity with higher, and there are octatomic ring ducts to intersect connection phenomenon, Crystal morphology is the cube that a triangular pyramid is all had at the center of six faces.Importantly, being synthesized by method of the invention Twin SAPO-34 molecular sieve in the reaction of methanol-to-olefins have show excellent catalytic performance, have preferable second The selectivity of light olefin of alkene and propylene.
According to the second aspect of the invention, the present invention provides a kind of synthetic methods of twin SAPO-34 molecular sieve, should Synthetic method is hydro-thermal method, wherein the synthetic method includes:
(1) a kind of mixed liquor is provided, the mixed liquor contains phosphorus source, silicon source, silicon source, template and water；
(2) mixed liquor is subjected to hydrothermal crystallizing；
(3) mixture for obtaining hydrothermal crystallizing is separated by solid-liquid separation, and obtained solid phase is dried and optionally Roasting.
The present invention also provides the synthetic method of another twin SAPO-34 molecular sieve, which is phosphorus aluminium Dry glue liquid phase conversion, wherein the synthetic method includes:
(1) mixed liquor A is provided, the mixed liquor A contains phosphorus source, silicon source and water；
(2) mixed liquor A is subjected to aging, then dried, phosphorus aluminium dry glue is made；
(3) raw mixture B is provided, the raw mixture B contains phosphorus aluminium dry glue, silicon source, template made from step (2) Agent and water；
(4) raw mixture B is subjected to hydrothermal crystallizing；
(5) mixture for obtaining hydrothermal crystallizing is separated by solid-liquid separation, and obtained solid phase is dried and optionally Roasting.
Above-mentioned synthetic method according to the present invention, the template are pyrrolidines, N- crassitude, 2- methylpyrrole At least one of alkane, 3- crassitude, 2,5- dimethyl pyrrolidine.
Herein, "at least one" indicates one or more kinds of.
According to the present invention, it is synthesized in twin SAPO-34 molecular sieve of the present invention using hydro-thermal method, it is described mixed preparing When closing liquid, phosphorus source is with P2O5Meter, source of aluminium is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus source, silicon source, silicon source, template The molar ratio of agent and water is 0.6-1.2:0.05-1.2:1:1.5-10:3-100, preferably 0.8-1.2:0.1-1:1:1.5-5: 5-50.Wherein, when preparing the mixed liquor, the water is total Water, it may for example comprise the water of addition further includes phosphorus source, silicon Water in source, silicon source and template.
According to the present invention, it is synthesized in twin SAPO-34 molecular sieve of the present invention using phosphorus aluminium dry glue liquid phase conversion, When preparing phosphorus aluminium dry glue, phosphorus source is with P2O5Meter, source of aluminium is with Al2O3Meter, the molar ratio of phosphorus source, silicon source and water are 0.6-1.2:1:20-70, preferably 0.8-1.2:1:20-60；When preparing raw mixture B, the phosphorus aluminium dry glue is with Al2O3 Meter, the silicon source is with SiO2Meter, phosphorus aluminium dry glue, silicon source, the molar ratio of template and water are as follows: 1:0.05-1.2:1.5-10:3- 100, preferably 1:0.1-1:1.5-5:5-50.Wherein, when preparing the mixed liquor A, the water is total Water, for example, Water including addition further includes phosphorus source, the water in silicon source.When preparing raw mixture B, the water is total Water, example It such as, further include the water in phosphorus aluminium dry glue, silicon source and template including the water of addition.
The type of phosphorus source, silicon source and silicon source is not particularly limited in the present invention, can be conventional selection.
Generally, phosphorus source can be selected from orthophosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and organic phosphorus compound At least one of.
Preferably, the organic phosphorus compound are at least one of trimethyl phosphorus and triethyl phosphine.
Source of aluminium can be in aluminium salt, boehmite, aluminium isopropoxide, aluminum hydroxide solid elastomer and activated alumina It is at least one.
Preferably, the aluminium salt is at least one of aluminium chloride and aluminum sulfate.
The silicon source can be selected from silica solution, active silica, solid silicone, silicon-containing compound shown in Formulas I and white At least one of carbon black,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, such as methyl, ethyl, propyl and its isomers and butyl and Its isomers.
Preferably, the silicon-containing compound is silica solution, active silica, solid silicone, ethyl orthosilicate and hard charcoal It is at least one of black.
According to the present invention, it is synthesized in twin SAPO-34 molecular sieve of the present invention using hydro-thermal method, it can be using conventional Method mixes phosphorus source, silicon source, silicon source, template and water, to obtain the mixed liquor.Specifically, can by silicon source, water, Phosphorus source, silicon source and template are sequentially added and are uniformly mixed, to obtain the mixed liquor.
According to the present invention, it is synthesized in twin SAPO-34 molecular sieve of the present invention using phosphorus aluminium dry glue liquid phase conversion, Phosphorus aluminium dry glue can be prepared using conventional method, and phosphorus aluminium dry glue, silicon source, template and water are mixed, to obtain the original Expect mixture B.Specifically, silicon source is mixed with water, then with stirring addition phosphorus source, obtains mixed liquor A, mixed liquor A is existed Stirring is lower to carry out aging, and aging temperature can be 50-80 DEG C, and preferably 60-70 DEG C, ageing time can be 6-20 hours, excellent It is selected as 10-18 hours, then the mixed liquor A after aging is dried, dry temperature can be 80-120 DEG C, preferably 80-100 DEG C, the dry time can be 12-36 hours, and preferably 20-30 hours, phosphorus aluminium dry glue is made.By phosphorus aluminium dry glue, silicon Source, water and template are sequentially added and are uniformly mixed, to obtain the raw mixture B.
According to the present invention, the hydrothermal crystallizing can carry out at conventional temperatures, such as 100-200 DEG C at a temperature of into Row.The time of the hydrothermal crystallizing may be conventional selection.
However, according to the method for the present invention, using previously described template, while using two sections of variable temperature crystallizations, also capable of There is the twin SAPO-34 molecular sieve of more high-crystallinity and more preferable MTO catalytic performance, preferable case with the preparation of higher yield Under, the hydrothermal crystallizing uses two sections of variable temperature crystallizations, that is, includes first segment crystallization and second segment crystallization, the temperature of first segment crystallization It can be 100-180 DEG C, the temperature of second segment crystallization can be 140-200 DEG C, it is further preferred that the temperature of first segment crystallization is 130- 170 DEG C, the temperature of second segment crystallization is 150-195 DEG C, and most preferably, the temperature of first segment crystallization is 140-160 DEG C, and second segment is brilliant The temperature of change is 160-190 DEG C.
The time of first segment crystallization can be 10-70 hours, and the time of second segment crystallization can be 3-80 hours, more excellent Choosing, the time of first segment crystallization are 20-60 hours, and the time of second segment crystallization is 4-60 hours, most preferably, first segment crystallization Time is 30-45 hours, and the time of second segment crystallization is 5-50 hours.
According to the present invention, the solid phase that mixture hydrothermal crystallizing obtained is separated by solid-liquid separation can be in normal condition Under be dried and optionally roast, to obtain twin SAPO-34 molecular sieve.It is " optional " to indicate inessential in the present invention, It can be understood as including or not including.Specifically, the drying can 80-120 DEG C at a temperature of carry out, the drying when Between can be selected according to dry temperature, generally can be 2-12 hours.The purpose of the roasting essentially consists in removing point Remain in the template in molecular sieve pore passage in son sieve synthesis process, can determine whether to be roasted according to specifically used requirement It burns.It is preferred that being roasted after the completion of drying.The roasting can 400-700 DEG C at a temperature of carry out, the roasting is held The continuous time can be selected according to the temperature of roasting, generally can be 2-8 hours.It is described roasting generally in air atmosphere into Row.Further, it is also possible to be washed obtained solid phase is separated by solid-liquid separation before the drying, that is, the mixing for obtaining hydrothermal crystallizing Object is separated by solid-liquid separation, washs (optional) and drying, and molecular screen primary powder can be obtained；Alternatively, the mixture that hydrothermal crystallizing is obtained into Row is separated by solid-liquid separation, washs (optional), dry (optional) and roast, the molecular sieve after can must roasting.Washing is generally in room temperature to 50 It is mixed or is eluted with water at DEG C, water is generally 1-20 times of hydrothermal crystallizing product quality.The method of the separation of solid and liquid It can be carried out using conventional method, such as filtering, centrifuge separation etc..
According to the present invention, to the heating mode of either step in the twin SAPO-34 Zeolite synthesis method without spy The mode of temperature programming, such as 0.5 DEG C -1 DEG C/min can be used in other limitation.
According to the present invention, not special to the hydrothermal crystallizing pressure in the twin SAPO-34 Zeolite synthesis method Limitation can be the self-generated pressure of crystallization system.
According to the third aspect of the present invention, the present invention provides a kind of method of methanol-to-olefins, this method is included in Under the conditions of methanol to olefins reaction, methanol is contacted with twin SAPO-34 molecular sieve provided by the invention.
Methanol-to-olefins method according to the present invention can carry out under the conditions of conventional methanol to olefins reaction, as long as Use twin SAPO-34 molecular sieve provided by the invention.Generally, can 400-500 DEG C at a temperature of by methanol with The contact of SAPO-34 molecular sieve.The weight space velocity of methanol can be 1-9h-1。
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, X-ray powder diffraction material phase analysis (XRD) is using Dutch Panaco Empyrean Type diffractometer, equipped with PIXcel3DDetector.Test condition: Cu target, K α radiation, Ni filter plate, tube voltage 40kV, pipe electricity Flow 40mA, 5 ° -50 ° of scanning range.
In following embodiment and comparative example, scanning electron microscope morphology analysis (SEM) is swept using Hitachi, Japan S4800 type Retouch Electronic Speculum.Test condition: it after sample drying milled processed, is sticked on conducting resinl.Analytic electron microscope accelerating potential is 5.0kV, 20-800000 times of amplification factor.
Template is represented with R in following embodiment.
Embodiment 1-12 synthesizes twin SAPO-34 molecule of the present invention using phosphorus aluminium dry glue liquid phase conversion for illustrating Sieve.
Embodiment 1
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 18.86 grams of deionized waters to equal Even, 9.22 grams of orthophosphoric acid (H are added in slow thread under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 60 DEG C, always Change 12 hours obtained mixture A.Mixture A is poured into pallet, dry 20 hours obtained phosphorus aluminium dry glues are placed at 80 DEG C.
Phosphorus aluminium dry glue (solid content 79.5%) made from taking 7.67 grams is added in polytetrafluoroethyllining lining, and sequentially adds 0.16 gram of solid silicone (SiO2Mass fraction 93%), 0.58 gram of deionized water, 4.34 grams of N- crassitude (C5H11N mass Score > 98%), stir evenly, the wherein addition molar ratio of each component are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.1, R/ Al2O3=2.0, H2O/Al2O3=5.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 30 hours, then be warming up to 160 DEG C, carry out second segment crystallization: 160 DEG C crystallization 15 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 1, it was demonstrated that be pure phase SAPO-34 molecule Sieve.It is observed using pattern of the SEM to molecular sieve, sample topography is twin pattern, is given birth at six faces center of cube A triangular pyramid is grown, SEM photograph is shown in Fig. 2.
Embodiment 2
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 11.66 grams of deionized waters to equal Even, 9.22 grams of orthophosphoric acid (H are added in slow thread under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 70 DEG C, always Change 12 hours obtained mixture A.Mixture A is poured into pallet, dry 24 hours obtained phosphorus aluminium dry glues are placed at 80 DEG C.
Phosphorus aluminium dry glue (solid content 83.3%) made from taking 7.32 grams is added in polytetrafluoroethyllining lining, sequentially adds 0.24 Gram solid silicone (SiO2Mass fraction 93%), 3.17 grams of deionized waters, 4.34 grams of 2- crassitude (C5H11N mass fraction 98%) it, stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.15, R/Al2O3 =2.0, H2O/Al2O3=10.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 35 hours, then be warming up to 160 DEG C, carry out second segment crystallization: 160 DEG C crystallization 10 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 3
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 26.06 grams of deionized waters to equal Even, 9.22 grams of orthophosphoric acid (H are added in slow thread under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 60 DEG C, always Change 12 hours obtained mixture A.Mixture A is poured into pallet, dry 24 hours obtained phosphorus aluminium dry glues are placed at 80 DEG C.
Phosphorus aluminium dry glue (solid content 81.4%) made from taking 7.49 grams is added in polytetrafluoroethyllining lining, sequentially adds 1.50 Gram silica solution (SiO2Mass fraction 30%), 6.49 grams of deionized waters, 3.26 grams of N- crassitude (C5H11N mass fraction > 98%) it, stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.3, R/Al2O3 =1.5, H2O/Al2O3=20.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 40 hours, then be warming up to 170 DEG C, carry out second segment crystallization: 170 DEG C crystallization 5 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Template used dose of N- crassitude is synthesized to the present embodiment and molecular sieve synthesis mother liquid carries out liquid13C MAS NMR analysis, the liquid of template N- crassitude13C MAS NMR spectra is shown in Fig. 3, the liquid of molecular sieve synthesis mother liquid13C MAS NMR spectra is shown in Fig. 4.Comparison is as it can be seen that used pyrrolidines template stable structure, in Zeolite synthesis mistake Cheng Zhong does not decompose.
Embodiment 4
By 4.91 boehmite (Al2O3Mass fraction 83%) it is stirred with 33.78 grams of deionized waters to uniform, In 9.22 grams of orthophosphoric acid (H are added in slow thread under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 70 DEG C, aging 12 Hour obtained mixture A.Mixture A is poured into pallet, dry 20 hours obtained phosphorus aluminium dry glues are placed at 80 DEG C.
Phosphorus aluminium dry glue (solid content 79.5%) made from taking 7.67 grams is added in polytetrafluoroethyllining lining, sequentially adds 0.81 Gram solid silicone (SiO2Mass fraction 93%), 11.84 grams of deionized waters, 2.69 grams of pyrrolidines (C4H9N mass fraction 99%), It stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.5, R/Al2O3=1.5, H2O/Al2O3=30.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 35 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 20 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 5
By 4.91 grams of boehmite (Al2O3Mass fraction 83%) it is stirred with 41.12 grams of deionized waters to uniform, 8.30 grams of orthophosphoric acid (H are added in slow thread under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 70 DEG C, aging 16 hours obtained mixture A.Mixture A is poured into pallet, dry 30 hours obtained phosphorus aluminium dry glues are placed at 90 DEG C.
Phosphorus aluminium dry glue (solid content 85.6%) made from taking 6.71 grams is added in polytetrafluoroethyllining lining, sequentially adds 4.00 Gram silica solution (SiO2Mass fraction 30%), 18.60 grams of deionized waters, 6.52 grams of 2- crassitude (C5H11N mass fraction 98%) it, stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=0.9, SiO2/Al2O3=0.8, R/Al2O3 =3.0, H2O/Al2O3=50.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 160 DEG C of crystalline substances at autogenous pressures Change 35 hours, then be warming up to 170 DEG C, carry out second segment crystallization: 170 DEG C crystallization 25 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 6
By 16.67 grams of aluminium isopropoxide (C9H21AlO3Mass fraction 98%) it is stirred with 34.28 grams of deionized waters to equal Even, 9.22 grams of orthophosphoric acid (H are added in slow thread under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 70 DEG C, always Change 16 hours obtained mixture A.Mixture A is poured into pallet, dry 24 hours obtained phosphorus aluminium dry glues are placed at 100 DEG C.
Phosphorus aluminium dry glue (solid content 92.6%) made from taking 7.38 grams is added in polytetrafluoroethyllining lining, sequentially adds 1.58 Gram ethyl orthosilicate (SiO2Mass fraction > 28%), 16.20 grams of deionized waters, 10.08 grams of 3- crassitude (C5H11N mass Score 95%), stir evenly, the wherein addition molar ratio of each component are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.3, R/ Al2O3=4.5, H2O/Al2O3=40.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 35 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 40 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 7
By 4.16 grams of activated alumina (Al2O3Mass fraction 98%) it is stirred with 34.39 grams of deionized waters to uniform, 10.15 grams of orthophosphoric acid (H are added in slow thread under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 60 DEG C, aging 16 hours obtained mixture A.Mixture A is poured into pallet, dry 24 hours obtained phosphorus aluminium dry glues are placed at 90 DEG C.
Phosphorus aluminium dry glue (solid content 89.7%) made from taking 7.19 grams is added in polytetrafluoroethyllining lining, sequentially adds 0.47 Gram active silica (SiO2Mass fraction 95%), 7.48 grams of deionized waters, 10.77 grams of 2,5- dimethyl pyrrolidine (C6H14N Mass fraction 93%), stir evenly, the wherein addition molar ratio of each component are as follows: P2O5/Al2O3=1.1, SiO2/Al2O3= 0.3、R/Al2O3=4.0, H2O/Al2O3=20.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 140 DEG C of crystalline substances at autogenous pressures Change 40 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 45 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 8
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 35.94 grams of deionized waters to equal Even, 11.81 grams of phosphorous acid (H are added in slow thread under stirring3PO3Mass fraction 50%), it is sufficiently stirred at 70 DEG C, Aging 10 hours obtained mixture A.Mixture A is poured into pallet, dry 24 hours obtained phosphorus aluminium dry glues are placed at 100 DEG C.
Phosphorus aluminium dry glue (solid content 93.1%) made from taking 6.17 grams is added in polytetrafluoroethyllining lining, sequentially adds 0.79 Gram ethyl orthosilicate (SiO2Mass fraction > 28%), 6.25 grams of deionized waters, 3.26 grams of N- crassitude (C5H11N mass point Several > 98%) it, stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=0.9, SiO2/Al2O3=0.15, R/ Al2O3=1.5, H2O/Al2O3=15.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 40 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 40 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 5, it was demonstrated that be pure phase SAPO-34 molecule Sieve.It is observed using pattern of the SEM to molecular sieve, sample topography is twin pattern, is given birth at six faces center of cube A triangular pyramid is grown, SEM photograph is shown in Fig. 6.
Embodiment 9
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 27.22 grams of deionized waters to equal It is even, 10.78 grams of ammonium hydrogen phosphate ((NH are slowly added under stirring4)2HPO4Mass fraction 98%), it is sufficiently stirred at 60 DEG C It mixes, aging 18 hours obtained mixture A.Mixture A is poured into pallet, it is dry to be placed at 90 DEG C dry 30 hours obtained phosphorus aluminium Glue.
Phosphorus aluminium dry glue (solid content 88.9%) made from taking 6.86 grams is added in polytetrafluoroethyllining lining, sequentially adds 0.31 Gram white carbon black (SiO2Mass fraction 98%), 3.67 grams of deionized waters, 3.26 grams of 2- crassitude (C5H11N mass fraction 98%) it, stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.2, R/Al2O3 =1.5, H2O/Al2O3=10.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 140 DEG C of crystalline substances at autogenous pressures Change 45 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 50 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 10
By 16.67 grams of aluminium isopropoxide (C9H21AlO3Mass fraction 98%) it is stirred with 35.45 grams of deionized waters to equal It is even, 10.78 grams of ammonium hydrogen phosphate ((NH are slowly added under stirring4)2HPO4Mass fraction 98%), it is sufficiently stirred at 70 DEG C It mixes, aging 14 hours obtained mixture A.Mixture A is poured into pallet, it is dry to be placed at 80 DEG C dry 24 hours obtained phosphorus aluminium Glue.
Phosphorus aluminium dry glue (solid content 76.6%) made from taking 7.96 grams is added in polytetrafluoroethyllining lining, sequentially adds 0.65 Gram solid silicone (SiO2Mass fraction 93%), 9.28 grams of deionized waters, 3.26 grams of N- crassitude (C5H11N mass fraction > 98%) it, stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.4, R/Al2O3 =1.5, H2O/Al2O3=25.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 36 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 45 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 7, it was demonstrated that be pure phase SAPO-34 molecule Sieve.It is observed using pattern of the SEM to molecular sieve, sample topography is twin pattern, is given birth at six faces center of cube A triangular pyramid is grown, SEM photograph is shown in Fig. 8.
Embodiment 11
By 4.91 grams of boehmite (Al2O3Mass fraction 83%) it is stirred with 35.09 grams of deionized waters to uniform, 7.44 grams of ammonium dihydrogen phosphate (NH are slowly added under stirring4H2PO4Mass fraction 99%), it is sufficiently stirred at 70 DEG C, always Change 14 hours obtained mixture A.Mixture A is poured into pallet, dry 24 hours obtained phosphorus aluminium dry glues are placed at 80 DEG C.
Phosphorus aluminium dry glue (solid content 80.2%) made from taking 6.72 grams is added in polytetrafluoroethyllining lining, sequentially adds 0.48 Gram solid silicone (SiO2Mass fraction 93%), 7.57 grams of deionized waters, 6.29 grams of pyrrolidines (C4H9N mass fraction 99%), stir It mixes uniformly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=0.8, SiO2/Al2O3=0.3, R/Al2O3=3.5, H2O/Al2O3=20.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 160 DEG C of crystalline substances at autogenous pressures Change 30 hours, then be warming up to 170 DEG C, carry out second segment crystallization: 170 DEG C crystallization 20 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 12
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) and 34.53 grams of deionized waters, it is stirred to equal It is even, 11.15 grams of ammonium dihydrogen phosphate (NH are slowly added under stirring4H2PO4Mass fraction 99%), it is sufficiently stirred at 70 DEG C It mixes, aging 12 hours obtained mixture A.Mixture A is poured into pallet, it is dry to be placed at 90 DEG C dry 24 hours obtained phosphorus aluminium Glue.
Phosphorus aluminium dry glue (solid content 83.7%) made from taking 8.13 grams is added in polytetrafluoroethyllining lining, sequentially adds 0.16 Gram solid silicone (SiO2Mass fraction 93%), 5.37 grams of deionized waters, 4.49 grams of pyrrolidines (C4H9N mass fraction 99%), stir It mixes uniformly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=1.2, SiO2/Al2O3=0.1, R/Al2O3=2.5, H2O/Al2O3=15.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 35 hours, then be warming up to 170 DEG C, carry out second segment crystallization: 170 DEG C crystallization 10 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 13-15 synthesizes twin SAPO-34 molecular sieve of the present invention using hydro-thermal method for illustrating.
Embodiment 13
By 3.40 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%), 0.44 gram of deionized water, 5.76 grams of orthophosphoric acid (H3PO4Mass fraction 85%), 0.16 gram of solid silicone (SiO2Mass fraction 93%), 4.34 grams of N- crassitude (C5H11N Mass fraction > 98%) it sequentially adds in polytetrafluoroethyllining lining, it stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/ Al2O3=1.0, SiO2/Al2O3=0.1, R/Al2O3=2.0, H2O/Al2O3=5.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 36 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 45 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, sample topography is twin pattern, is grown at six faces center of cube A triangular pyramid out.
Embodiment 14
By 3.07 grams of boehmite (Al2O3Mass fraction 83%), 18.27 grams of deionized waters, 5.19 grams of orthophosphoric acid (H3PO4Mass fraction 85%), 4.00 grams of silica solution (SiO2Mass fraction 30%), 6.52 grams of 2- crassitude (C5H11N matter Amount score 98%) it sequentially adds in polytetrafluoroethyllining lining, it stirs evenly, wherein the addition molar ratio of each component are as follows: P2O5/ Al2O3=0.9, SiO2/Al2O3=0.8, R/Al2O3=3.0, H2O/Al2O3=50.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 160 DEG C of crystalline substances at autogenous pressures Change 35 hours, then be warming up to 170 DEG C, carry out second segment crystallization: 170 DEG C crystallization 25 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 9, it was demonstrated that be pure phase SAPO-34 molecule Sieve.It is observed using pattern of the SEM to molecular sieve, sample topography is twin pattern, is given birth at six faces center of cube A triangular pyramid is grown, SEM photograph is shown in Figure 10.
Embodiment 15
By 10.42 grams of aluminium isopropoxide (C9H21AlO3Mass fraction 98%), 10.80 grams of deionized waters, 6.74 grams of phosphoric acid hydrogen Ammonium ((NH4)2HPO4Mass fraction 98%), 0.65 gram of solid silicone (SiO2Mass fraction 93%), 3.26 grams of N- crassitudes (C5H11N mass fraction > 98%) it sequentially adds in polytetrafluoroethyllining lining, it stirs evenly, wherein the addition molar ratio of each component Are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.4, R/Al2O3=1.5, H2O/Al2O3=25.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 36 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 45 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Figure 11, it was demonstrated that be pure phase SAPO-34 molecule Sieve.It is observed using pattern of the SEM to molecular sieve, sample topography is twin pattern, is given birth at six faces center of cube A triangular pyramid is grown, SEM photograph is shown in Figure 12.
Comparative example 1
This comparative example explanation synthesizes SAPO-34 molecular sieve using reference method.
SAPO-34 molecular sieve is synthesized according to the method for embodiment 3, difference is this comparative example without using N- crassitude Make template, but synthesizes most commonly used triethylamine using SAPO-34 and make template.
By 5.44 grams of aluminum hydroxide solid elastomer (Al2O3Mass fraction 75%) it is stirred with 26.06 grams of deionized waters to equal Even, 9.22 grams of orthophosphoric acid (H are added in slow thread under stirring3PO4Mass fraction 85%), it is sufficiently stirred at 60 DEG C, always Change 12 hours obtained mixture A.Mixture A is poured into pallet, dry 25 hours obtained phosphorus aluminium dry glues are placed at 80 DEG C.
Phosphorus aluminium dry glue (solid content 81.4%) made from taking 7.49 grams is added in polytetrafluoroethyllining lining, sequentially adds 1.50 Gram silica solution (SiO2Mass fraction 30%), 6.52 grams of deionized waters, 3.83 grams of triethylamine (C6H15N mass fraction 99%), stir It mixes uniformly, wherein the addition molar ratio of each component are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.3, R/Al2O3=1.5, H2O/Al2O3=20.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 40 hours, then be warming up to 170 DEG C, carry out second segment crystallization: 170 DEG C crystallization 5 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis and the pattern of molecular sieve is observed using SEM, is characterized The result shows that sample is pure phase SAPO-34 molecular sieve, SEM photograph is shown in that Figure 13, display sample topography are conventional cube pattern.
Comparative example 2
This comparative example explanation synthesizes SAPO-34 molecular sieve using reference method.
SAPO-34 molecular sieve is synthesized according to the method for embodiment 15, difference is this comparative example without using N- methylpyrrole Alkane makees template, but synthesizes most commonly used tetraethyl ammonium hydroxide using SAPO-34 and make template.
By 10.42 grams of aluminium isopropoxide (C9H21AlO3Mass fraction 98%), 0.61 gram of deionized water, 6.74 grams of ammonium hydrogen phosphates ((NH4)2HPO4Mass fraction 98%), 0.65 gram of solid silicone (SiO2Mass fraction 93%), 15.78 grams of tetraethyl hydroxides Ammonium (C8H21NO mass fraction 35%) it sequentially adds in polytetrafluoroethyllining lining, it stirs evenly, wherein the addition mole of each component Than are as follows: P2O5/Al2O3=1.0, SiO2/Al2O3=0.4, R/Al2O3=1.5, H2O/Al2O3=25.
Polytetrafluoroethyllining lining equipped with above-mentioned reaction mixture is covered, is put into stainless steel autoclave and seals, by this Autoclave is placed in rotation convection oven, and revolving speed is set as 20r/min, carries out first segment crystallization: 150 DEG C of crystalline substances at autogenous pressures Change 36 hours, then be warming up to 180 DEG C, carry out second segment crystallization: 180 DEG C crystallization 45 hours, completed to crystallization, autoclave temp drop Crystallization product is taken out when to room temperature, is filtered or is centrifugated, is washed with deionized, 110 DEG C of dryings obtain solid in 12 hours Product, as molecular screen primary powder.
Obtained molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Figure 14, it was demonstrated that be pure phase SAPO-34 molecule Sieve.It is observed using pattern of the SEM to molecular sieve, sample topography is conventional cube pattern, and SEM photograph is shown in Figure 15.
Embodiment 16-19
Embodiment 16-19 is for illustrating methanol-to-olefins method of the invention.
Embodiment 16-19 illustrates anti-in methanol-to-olefins using embodiment 8,10,14 and 15 gained sieve samples respectively Catalytic performance result in answering.
Embodiment 8,10,14 and 15 resulting molecular screen primary powders are placed in program in Muffle furnace respectively and are warming up to 550 DEG C of roastings Burn the sample after roast for 3 hours, be sieved through tabletting, the sample of selection 20-40 mesh, be respectively labeled as S-1, S-2, S-3 and S-4。
It is put into fixed bed reactors using 3g sieve sample S-1, S-2, S-3 and S-4 as catalyst respectively, 500 Lead at DEG C nitrogen activation 0.5 hour, is then cooled to 450 DEG C, reaction pressure 0.1MPa.The pure methanol of raw material passes through flow measurement Enter preheating furnace after pump under the carrying as the nitrogen of carrier gas, and be vaporized into gas in preheating furnace, subsequently into fixed bed It is reacted in reactor.Wherein, nitrogen flow 350mL/min, the weight space velocity of methanol are 1h-1。
Reaction product is with ethylene (C2=) and propylene (C3=) it is target product, reaction product is by Agilent GC7890A gas phase On-line chromatographic analysis, the results are shown in Table 1 for MTO catalytic performance.
Comparative example 3
Comparative example 3 is used to illustrate the reference method of methanol-to-olefins.
The explanation of comparative example 3 uses catalytic performance result of the 2 gained sieve sample of comparative example in methanol to olefins reaction.
It the resulting molecular screen primary powder of comparative example 2 is placed in program in Muffle furnace is warming up to 550 DEG C of roastings and roasted for 3 hours Sample afterwards, is sieved through tabletting, chooses the sample of 20-40 mesh, is labeled as D-1.Evaluation method and condition and embodiment 16-19 phase Together, the results are shown in Table 1 for MTO catalytic performance.
Table 1
As seen from Table 1, the zeolite product that the present invention synthesizes has a longer life expectancy and higher double Alkene selectivity, wherein the diene selective of S-1 is up to 86.63%, illustrates the twin pattern SAPO-34 molecular sieve that the present invention synthesizes With preferable MTO catalytic performance.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (17)

1. a kind of twin SAPO-34 molecular sieve, which is characterized in that the crystal morphology of the twin SAPO-34 molecular sieve is six The cube of a triangular pyramid is all had at the center of face.
2. the synthetic method of twin SAPO-34 molecular sieve described in claim 1, which is characterized in that the synthetic method includes:
(1) a kind of mixed liquor is provided, the mixed liquor contains phosphorus source, silicon source, silicon source, template and water, and phosphorus source is with P2O5 Meter, source of aluminium is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus source, silicon source, silicon source, the molar ratio of template and water are 0.6- 1.2:0.05-1.2:1:1.5-10:3-100；
(2) mixed liquor is subjected to hydrothermal crystallizing；
(3) mixture for obtaining hydrothermal crystallizing is separated by solid-liquid separation, and obtained solid phase is dried and is optionally roasted；
Wherein, the template is pyrrolidines, N- crassitude, 2- crassitude, 3- crassitude and 2,5- diformazan At least one of base pyrrolidines.
3. synthetic method according to claim 2, wherein phosphorus source, silicon source, silicon source, the molar ratio of template and water are 0.8-1.2:0.1-1:1:1.5-5:5-50。
4. the synthetic method of twin SAPO-34 molecular sieve described in claim 1, which is characterized in that the synthetic method includes:
(1) mixed liquor A is provided, the mixed liquor A contains phosphorus source, silicon source and water, and phosphorus source is with P2O5Meter, source of aluminium with Al2O3Meter, the molar ratio of phosphorus source, silicon source and water are 0.6-1.2:1:20-70；
(2) mixed liquor A is subjected to aging, then dried, phosphorus aluminium dry glue is made；
(3) provide raw mixture B, the raw mixture B contain phosphorus aluminium dry glue made from step (2), silicon source, template and Water, the phosphorus aluminium dry glue is with Al2O3Meter, the silicon source is with SiO2Meter, phosphorus aluminium dry glue, silicon source, the molar ratio of template and water are as follows: 1:0.05-1.2:1.5-10:3-100；
(4) raw mixture B is subjected to hydrothermal crystallizing；
(5) mixture for obtaining hydrothermal crystallizing is separated by solid-liquid separation, and obtained solid phase is dried and is optionally roasted；
Wherein, the template is pyrrolidines, N- crassitude, 2- crassitude, 3- crassitude and 2,5- diformazan At least one of base pyrrolidines.
5. synthetic method according to claim 4, wherein the molar ratio of phosphorus source, silicon source and water is 0.8-1.2:1:20- 60；
Phosphorus aluminium dry glue, silicon source, the molar ratio of template and water are 1:0.1-1:1.5-5:5-50.
6. the synthetic method according to any one of claim 2-5, wherein the hydrothermal crystallizing includes first segment crystallization With second segment crystallization, first segment crystallization is crystallization 10-70 hours at 100-180 DEG C, second segment crystallization crystallization at 140-200 DEG C 3-80 hours.
7. synthetic method according to claim 6, wherein first segment crystallization crystallization 20-60 hours at 130-170 DEG C, Second segment crystallization is crystallization 4-60 hours at 150-195 DEG C.
8. synthetic method according to claim 7, wherein first segment crystallization crystallization 30-45 hours at 140-160 DEG C, Second segment crystallization is crystallization 5-50 hours at 160-190 DEG C.
9. the synthetic method according to any one of claim 2-5, wherein phosphorus source be selected from orthophosphoric acid, phosphorous acid, At least one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate and organic phosphorus compound,
The organic phosphorus compound are at least one of trimethyl phosphorus and triethyl phosphine.
10. the synthetic method according to any one of claim 2-5, wherein source of aluminium is selected from aluminium salt, intends thin water aluminium At least one of stone, aluminium isopropoxide, aluminum hydroxide solid elastomer and activated alumina,
The aluminium salt is at least one of aluminium chloride and aluminum sulfate.
11. the synthetic method according to any one of claim 2-5, wherein the silicon source is selected from silica solution, activity two Silica, solid silicone, at least one of silicon-containing compound and white carbon black shown in Formulas I,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl.
12. synthetic method according to claim 11, wherein the silicon-containing compound is ethyl orthosilicate.
13. synthetic method according to claim 4 or 5, wherein mixed liquor A is carried out aging under stiring in step (2) It carries out, aging temperature is 50-80 DEG C, and ageing time is 6-20 hours；Dry temperature is 80-120 DEG C, and the dry time is 12-36 hours.
14. synthetic method according to claim 13, wherein aging temperature is 60-70 DEG C, and ageing time is that 10-18 is small When；Dry temperature is 80-100 DEG C, and the dry time is 20-30 hours.
15. the synthetic method according to any one of claim 2-5, wherein the temperature that obtained solid phase is dried Degree is 80-120 DEG C, and the temperature of the roasting is 400-700 DEG C.
16. a kind of method of methanol-to-olefins, this method are included under the conditions of methanol to olefins reaction, by methanol and claim The twin that the 1 twin SAPO-34 molecular sieve or the synthetic method as described in any one of claim 2-15 obtain The contact of SAPO-34 molecular sieve.
17. according to the method for claim 16, wherein it is described contact 400-500 DEG C at a temperature of carry out, the weight of methanol Amount air speed is 1-9h-1。
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