CN104556093A - Preparation method of small-grain SAPO-34 molecular sieve - Google Patents
Preparation method of small-grain SAPO-34 molecular sieve Download PDFInfo
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- CN104556093A CN104556093A CN201410830670.6A CN201410830670A CN104556093A CN 104556093 A CN104556093 A CN 104556093A CN 201410830670 A CN201410830670 A CN 201410830670A CN 104556093 A CN104556093 A CN 104556093A
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- molecular sieve
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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
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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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- 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
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- 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
Abstract
The invention relates to a preparation method of a small-grain SAPO-34 molecular sieve. The preparation method comprises the following steps: mixing an aluminum source and a phosphorus source with deionized water, stirring for 1-5 h, then adding a silicon source, an organic amine template agent R, an auxiliary template agent R' and an organic solvent A, continuously stirring for 1-5 h to obtain a gel, transferring the gel into a crystallization kettle, crystallizing for 12-108 h at the temperature of 160-220 DEG C to obtain a mixed liquor, filtering the mixed liquor to obtain a filter cake, washing the filter cake with deionized water, drying, and roasting to obtain an SAPO-34 molecular sieve. On the basis of using a conventional organic amine template agent, a small amount of auxiliary template agent R' and organic solvent A are added, and the cube-shaped SAPO-34 molecular sieve which is high in degree of crystallinity, regular in crystal form and 0.2 microns in grain size is successfully prepared through a hydrothermal crystallization method; moreover, the method is simple in procedures and easy to operate, the SAPO-34 molecular sieve has a great industrialization development prospect, and is expected to be used as a catalyst for preparing low-carbon olefinethrough methanol conversio and a catalyst for treating automobile exhaust.
Description
Technical field
The present invention relates to a kind of preparation method of fine grain SAPO-34 molecular sieve, belong to chemical field.
Background technology
SAPO-34 is by SiO
2, AlO
2-, PO
2+, the microporous crystals that three kinds of tetrahedron elements are formed, according to the regulation of international zeolite and molecular sieve association (IZA), belongs to CHA structure.Although the time that SAPO-34 occurs is not long, but because it has suitable pore passage structure, suitable acidity and high hydrothermal stability, and in methanol to olefins reaction (MTO), show the catalytic performance more excellent than ZSM-5 and selectivity of light olefin, be therefore considered to desirable MTO catalyzer.Along with deepening continuously of research, numerous scientific documents shows, SAPO-34 is at SCR (SCR) NO
xin also can play important katalysis, be the novel exhaust gas treatment catalyst of current very potential one.
The grain-size of catalyzer is the important factor affecting catalyst activity and work-ing life.The molecular sieve of little grain-size has larger specific surface area, is conducive to the carrying out of catalysis; It also has relatively short internal gutter simultaneously, is conducive to the diffusion of reactant and product, can effectively suppresses excessive catalysis, reduces carbon distribution speed, the extending catalyst life-span.Therefore, the favor of the molecular sieve of little grain-size extremely researcher.
At present, multiple means is had to prepare fine grain SAPO-34 molecular sieve.
Liping Ye etc. [J Porous Mater (2011) 18:225-232] use TEAOH to prepare specific surface area up to 781m for template
2/ g, the little grain-size SAPO-34 of grain-size between 300-800nm.But TEAOH is expensive, causes SAPO-34 cost higher, be unfavorable for the marketization.
Yuichiro Hirota etc. [Materials Chemistry and Physics 123 (2010) 507-509] are template with TEAOH, adopt dry glue process to prepare the SAPO-34 molecular sieve of grain-size at about 75nm.Although the method effectively can reduce grain-size, operation steps is more, and crystallization system used amplifies difficulty, is unfavorable for industrial production.
Patent CN103130241A reduces crystallization temperature by microwave heating or shortens crystallization time, then introduces the object that suitable dispersion agent reaches reduction grain-size, prepares the SAPO-34 molecular sieve that grain-size is 100nm.Although lot of documents shows, compared with traditional hydrothermal crystallization method, the chemical reaction that microwave heating method generation internal heat effect facilitates in solution carries out, and it is very even to make whole system heat up, be conducive to the formation of fine grain SAPO-34 molecular sieve, but microwave heating method is only applicable to small scale experiments, be not suitable for scale operation, be difficult to carry out industry and amplify.
It is aging that patent CN101214974A carries out ultrasonic wave in colloidal sol preparation process simultaneously, and crystallization obtains the SAPO-34 molecular sieve of grain-size between 0.5-1.5 μm under hydrothermal conditions.Although ultrasonic wave burin-in process can reduce grain-size, the method still faces device and amplifies difficulty, is unfavorable for industrial problem.
In sum, existing document and patent report are mainly through using TEAOH to be template, adopting dry glue process, adopting the mode such as microwave heating method or ultrasonic wave weathering process to obtain the SAPO-34 molecular sieve of little crystal grain.Above method is all unfavorable for amplifying produces, and is limiting its industrial applications in varying degrees.Therefore, development technology preparation method that is simple, that be easy to the fine grain SAPO-34 molecular sieve that industry is amplified can better address this problem.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of fine grain SAPO-34 molecular sieve, overcomes existing fine grain SAPO-34 preparation method cost high, and preparation technology is difficult to the problems such as industry amplification.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of preparation method of fine grain SAPO-34 molecular sieve, comprising:
1) each raw material is taken by following molar ratio of material,: (50 ~ 100) organic amine template R: auxiliary template agent R ': phosphorus source: silicon source: aluminium source: organic solvent A: deionized water=(3 ~ 5): (0 ~ 1): (1.8 ~ 2.2): (0.3 ~ 0.6): 1:(0 ~ 2), wherein, described phosphorus source is with H
3pO
4molar weight calculate, described silicon source is with SiO
2molar weight calculate, described aluminium source is with Al
2o
3molar weight calculate;
Aluminium source, phosphorus source are mixed with deionized water, stirs 1 ~ 5h, then add silicon source, organic amine template R, auxiliary template agent R ' and organic solvent A, continue stirring 1 ~ 5h, obtain gel, gel is transferred in crystallizing kettle, 160 ~ 220 DEG C of crystallization 12 ~ 108h, obtain mixed solution, filter mixed liquor, obtains filter cake, deionized water wash filter cake is used while filtration, drying, roasting, obtains SAPO-34 molecular sieve.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described organic amine template R is the mixture of one or more in triethylamine, diethylamine, morpholine;
Further, described auxiliary template agent R ' is quaternary ammonium hydroxide or quaternary ammonium salt, be preferably hydroxide N, N, N-trimethylammonium-outer aminonorbornane amine (TMAmOH), halogenation N, N, N-trimethylammonium-outer aminonorbornane amine TMAmX (X=Cl or Br), hydroxide N, N, N-trimethylammonium amantadine (TMAdOH), halogenation N, a kind of or several arbitrarily mixture in N, N-trimethylammonium amantadine TMAdX (X=Cl or Br), hydroxide N-methyl-3-quinoline core alcohol.
Further, described phosphorus source is ortho-phosphoric acid;
Further, described aluminium source is the mixture of one or more in pseudo-boehmite, aluminium hydroxide, aluminum isopropylate;
Further, described silicon source is the mixture of one or more in silicon sol, tetraethoxy, white carbon black;
Further, described organic solvent A is the mixture of one or more in ethanol, ethyl acetate, tetrahydrofuran (THF), normal hexane, normal heptane, octane, toluene, dioxane.
Further, described washing leaching cake is less than 8 to the pH value of filtrate.
Further, described drying is 80 ~ 120 DEG C of drying 3 ~ 8h.
Further, described roasting refers to temperature rise rate temperature programming to 500 ~ 700 DEG C with 1 ~ 3 DEG C/min, insulation 5 ~ 6h.
The invention has the beneficial effects as follows:
The present invention uses cheap organic amine to be master module agent, add a small amount of auxiliary template agent R ', organic solvent A, degree of crystallinity has successfully been prepared high by hydrothermal crystallization method, regular crystal forms, the little cubic SAPO-34 molecular sieve to 0.2 μm of grain-size, the method step is simple simultaneously, easy handling, there is great industrialization development prospect, be expected to the catalyzer preparing low-carbon alkene and vehicle maintenance service as methanol conversion.
Accompanying drawing explanation
Fig. 1 is the XRD figure of embodiment 1 sample SAPO-34;
Fig. 2 is the SEM figure of embodiment 1 sample SAPO-34;
Fig. 3 is the XRD figure of embodiment 2 sample SAPO-34;
Fig. 4 is the SEM figure of embodiment 2 sample SAPO-34;
Fig. 5 is the XRD figure of embodiment 3 sample SAPO-34;
Fig. 6 is the SEM figure of embodiment 3 sample SAPO-34.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Under stirring at room temperature state, by 231.3g aluminum isopropylate (Al
2o
3content is 26.3%) drop in 682g deionized water, slowly drip 137.4g ortho-phosphoric acid (H subsequently
3pO
4content is 85%), after stirring 2h, add 71.4g silicon sol (SiO
2content is 30%), 266.4g triethylamine, 81.6gTMAmOH solution (TMAmOH content is 25%) and 51.3g normal hexane, form homogeneous gel after stirring 3h; Subsequently gel is transferred in 2L crystallizing kettle, 180 DEG C of insulation crystallization 48h under 120rpm whipped state.After crystallization completes, obtain mixed solution, filter mixed liquor, obtain filter cake, while filtering, be less than 8 by deionized water wash filter cake to the pH value of filtrate, dry 3 ~ 8h at 80 ~ 120 DEG C, at 550 ~ 600 DEG C, roasting 5 ~ 6h, obtains target product, called after A.Find through XRD, SEM characterization test, product A has CHA characteristic diffraction peak, and as shown in Figure 1, SEM picture is grain-size at the cubes crystal grain of 0.1 ~ 0.3 μm, as shown in Figure 2.
Embodiment 2
Under stirring at room temperature state, by 105.8g pseudo-boehmite (Al
2o
3content is 76.5%) drop in 884.8g deionized water, add 183.0g ortho-phosphoric acid (H
3pO
4content is 85%), after stirring 2h, add 95.2g silicon sol (SiO
2content is 30%), 355.2g triethylamine and 54.5gTMAmOH solution (TMAmOH content is 25%), form homogeneous gel after stirring 3h; Subsequently gel is transferred in 2L crystallizing kettle, 190 DEG C of insulation crystallization 48h under 120rpm whipped state.After crystallization completes, by mixed solution, filter mixed liquor, obtains filter cake, and while filtering, be less than 8 by deionized water wash filter cake to the pH value of filtrate, dry 3 ~ 8h at 80 ~ 120 DEG C, at 550 ~ 600 DEG C, roasting 5 ~ 6h, obtains target product, called after B.Find through XRD, SEM characterization test, product B has CHA characteristic diffraction peak, and as shown in Figure 3, SEM picture is grain-size at the cubes crystal grain of 0.3 ~ 0.8 μm, as shown in Figure 4.
Embodiment 3
Under stirring at room temperature state, by 96.8g pseudo-boehmite (Al
2o
3content is 76.5%) drop in 813g deionized water, add 168.3g ortho-phosphoric acid (H
3pO
4content is 85%), after stirring 2h, add 86.9g silicon sol (SiO
2content is 30%), 216.7g triethylamine, 49.9gTMAmOH solution (TMAmOH content is 25%) and 67.1g toluene, form homogeneous gel after stirring 3h; Subsequently gel is transferred in 2L crystallizing kettle, 200 DEG C of insulation crystallization 48h under 120rpm whipped state.After crystallization completes, obtain mixed solution, filter mixed liquor, obtain filter cake, while filtering, be less than 8 by deionized water wash filter cake to the pH value of filtrate, dry 3 ~ 8h at 80 ~ 120 DEG C, at 550 ~ 600 DEG C, roasting 5 ~ 6h, obtains target product, called after C.Find through XRD, SEM characterization test, products C has CHA characteristic diffraction peak, and as shown in Figure 5, SEM picture is grain-size at the cubes crystal grain of 0.8 ~ 1.2 μm, as shown in Figure 6.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a preparation method for fine grain SAPO-34 molecular sieve, is characterized in that, comprising:
1) each raw material is taken by following molar ratio of material,: (50 ~ 100) organic amine template R: auxiliary template agent R ': phosphorus source: silicon source: aluminium source: organic solvent A: deionized water=(3 ~ 5): (0 ~ 1): (1.8 ~ 2.2): (0.3 ~ 0.6): 1:(0 ~ 2), wherein, described phosphorus source is with H
3pO
4molar weight calculate, described silicon source is with SiO
2molar weight calculate, described aluminium source is with Al
2o
3molar weight calculate;
Aluminium source, phosphorus source are mixed with deionized water, stirs 1 ~ 5h, then add silicon source, organic amine template R, auxiliary template agent R ' and organic solvent A, continue stirring 1 ~ 5h, obtain gel, gel is transferred in crystallizing kettle, 160 ~ 220 DEG C of crystallization 12 ~ 108h, obtain mixed solution, filter mixed liquor, obtains filter cake, deionized water wash filter cake is used while filtration, drying, roasting, obtains SAPO-34 molecular sieve.
2. preparation method according to claim 1, is characterized in that, described organic amine template R is the mixture of one or more in triethylamine, diethylamine, morpholine;
Described auxiliary template agent R ' is quaternary ammonium hydroxide or quaternary ammonium salt;
Described phosphorus source is ortho-phosphoric acid;
Described aluminium source is the mixture of one or more in pseudo-boehmite, aluminium hydroxide, aluminum isopropylate;
Described silicon source is the mixture of one or more in silicon sol, tetraethoxy, white carbon black;
Described organic solvent A is the mixture of one or more in ethanol, ethyl acetate, tetrahydrofuran (THF), normal hexane, normal heptane, octane, toluene, dioxane.
3. preparation method according to claim 1 and 2, is characterized in that, described washing leaching cake is less than 8 to the pH value of filtrate.
4. preparation method according to claim 3, is characterized in that, described drying is 80 ~ 120 DEG C of drying 3 ~ 8h.
5. preparation method according to claim 4, is characterized in that, described roasting refers to temperature rise rate temperature programming to 500 ~ 700 DEG C with 1 ~ 3 DEG C/min, insulation 5 ~ 6h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036153A (en) * | 2015-07-17 | 2015-11-11 | 中国天辰工程有限公司 | Modification method of SAPO-34 molecular sieve |
| CN105399109A (en) * | 2015-12-18 | 2016-03-16 | 西安元创化工科技股份有限公司 | Preparation method and applications of small crystalline grain silicoaluminophosphate molecular sieve |
| CN105883850A (en) * | 2016-04-06 | 2016-08-24 | 中国天辰工程有限公司 | Preparation method of empty-shell type SAPO-34 molecular sieves |
| CN108298550A (en) * | 2018-04-12 | 2018-07-20 | 正大能源材料(大连)有限公司 | A method of it is mixed using tetrahydrofuran as template with organic amine and prepares multi-stage porous SAPO-34 molecular sieves |
| CN109704365A (en) * | 2019-02-22 | 2019-05-03 | 山东齐鲁华信高科有限公司 | A kind of fast synthesis method of small crystal grain molecular sieve and application |
| CN110240179A (en) * | 2018-03-09 | 2019-09-17 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve and its preparation method and application |
| CN112517058A (en) * | 2019-09-18 | 2021-03-19 | 中国石油化工股份有限公司 | AEI type molecular sieve and preparation method and application thereof |
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| CN101125665A (en) * | 2007-08-08 | 2008-02-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN104058425A (en) * | 2014-06-20 | 2014-09-24 | 烟台万润精细化工股份有限公司 | Preparation method of SAPO-34 molecular sieve |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036153A (en) * | 2015-07-17 | 2015-11-11 | 中国天辰工程有限公司 | Modification method of SAPO-34 molecular sieve |
| CN105399109A (en) * | 2015-12-18 | 2016-03-16 | 西安元创化工科技股份有限公司 | Preparation method and applications of small crystalline grain silicoaluminophosphate molecular sieve |
| CN105399109B (en) * | 2015-12-18 | 2018-06-12 | 西安元创化工科技股份有限公司 | A kind of preparation method and application of little crystal grain silicoaluminophosphamolecular molecular sieves |
| CN105883850A (en) * | 2016-04-06 | 2016-08-24 | 中国天辰工程有限公司 | Preparation method of empty-shell type SAPO-34 molecular sieves |
| CN110240179A (en) * | 2018-03-09 | 2019-09-17 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve and its preparation method and application |
| CN108298550A (en) * | 2018-04-12 | 2018-07-20 | 正大能源材料(大连)有限公司 | A method of it is mixed using tetrahydrofuran as template with organic amine and prepares multi-stage porous SAPO-34 molecular sieves |
| CN109704365A (en) * | 2019-02-22 | 2019-05-03 | 山东齐鲁华信高科有限公司 | A kind of fast synthesis method of small crystal grain molecular sieve and application |
| CN109704365B (en) * | 2019-02-22 | 2022-09-20 | 山东齐鲁华信高科有限公司 | Rapid synthesis method and application of small-grain molecular sieve |
| CN112517058A (en) * | 2019-09-18 | 2021-03-19 | 中国石油化工股份有限公司 | AEI type molecular sieve and preparation method and application thereof |
| CN112517058B (en) * | 2019-09-18 | 2023-07-04 | 中国石油化工股份有限公司 | AEI type molecular sieve and preparation method and application thereof |
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