CN108584982A - A method of synthesizing flat SSZ-13 molecular sieves with mixed templates - Google Patents
A method of synthesizing flat SSZ-13 molecular sieves with mixed templates Download PDFInfo
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- CN108584982A CN108584982A CN201810715502.0A CN201810715502A CN108584982A CN 108584982 A CN108584982 A CN 108584982A CN 201810715502 A CN201810715502 A CN 201810715502A CN 108584982 A CN108584982 A CN 108584982A
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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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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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
Abstract
The invention discloses a kind of preparation methods synthesizing 13 molecular sieves of flat SSZ with mixed templates.Tetrahydrofuran is mixed with adamantane ammonium hydroxide first and is used as mixed templates, sodium hydroxide dissolving is formed into sodium hydroxide solution in deionized water, then mixed templates are added to and are sufficiently stirred to form mixed solution in sodium hydroxide solution.It then sequentially adds in silicon source, silicon source to mixed solution, stirring a period of time forms homogeneous gel mixture.Obtained homogeneous gel mixture is transferred in hydrothermal reaction kettle, for a period of time, room temperature cools down crystallization after the completion of crystallization at a certain temperature, and solid product is washed by deionized water, is dry, then it is roasted in air to get to 13 molecular sieves of flat SSZ under 560 ° of С.13 molecular sieves of SSZ that the present invention synthesizes have flat pattern, and the crystal morphology of formation is regular, and solid phase yield is high, is of great significance for the commercial introduction application of 13 molecular sieves of SSZ.
Description
Technical field
The present invention relates to a kind of methods synthesizing flat SSZ-13 molecular sieves with mixed templates, belong to sieve technology
Field.
Background technology
Low-carbon alkene is basic chemical raw materials important in modern chemical industry, and with the development of modern industry to it
Demand is increasing.Ethylene, propylene tradition to produce mode be petroleum cracking, asked it is contemplated that petroleum resources are limited etc.
Topic, it is rear to propose to replace traditional handicraft by the method for methanol producing olefinic hydrocarbons.Methanol-to-olefins（MTO）Key be catalyst
Selection, the catalyst that can be used for methanol-to-olefins have chabasie, erionite, ZK-5 molecular sieves etc., but due to the limit of pore structure
System, it is easy to which forming carbon distribution leads to catalyst inactivation.SSZ-13 molecular sieves belong to CHA type molecular sieves, with SAPO-34 molecular sieve categories
In similar.SSZ-13 molecular sieves have preferable thermal stability, while having cationic exchangeability and acid adjustability, therefore
There is preferable catalytic performance during very much.Additionally due to the features such as its pore size is small, and specific surface area is high, is catalyzed in MTO
Also there is preferable catalytic performance in reaction, there is higher selectivity of light olefin.But since SSZ-13 molecular sieves have
Stronger acidity so that its MTO byproduct in process object is more, and is easy to carbon distribution and causes rapid deactivation so that the molecular sieve longevity
Life is shorter.Therefore how to regulate and control the acidity of SSZ-13 molecular sieves and extend its service life to be of great significance.
There is researcher to study this, proposes that the silica alumina ratio of regulatory molecule sieve can regulate and control its acidity, Mark E.
Davis etc. is published on ACS Catalysis the MTO catalysis reactions that SSZ-13 molecular sieves are had studied with an article for 2016
Performance, and the silica alumina ratio for improving SSZ-13 molecular sieves carries out MTO performance tests, as a result, it has been found that improving SSZ-13 molecular sieve silica alumina ratios
Its service life can be extended, and improve the selectivity of low-carbon alkene.It can be seen that the silica alumina ratio of molecular sieve is to catalysis reactivity
There can be great influence.About MTO performance tests, it is SAPO-34 molecular sieves to study more, to the research of SSZ-13 molecular sieves compared with
It is few, therefore SSZ-13 molecular sieves can regulate and control its silica alumina ratio, change its pattern, improve its catalytic performance, and MTO is reacted, is
One kind has the catalyst of potential using value.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies of existing technologies, one kind is provided and is synthesized with mixed templates
The method of flat SSZ-13 molecular sieves, this method use mixed templates, reduce the amount of amantadine ammonium hydroxide, reduce
Production cost, in addition, the SSZ-13 molecular sieves that thus synthesize have flat pattern, and its solid phase yield is high, crystal shape
Looks are good, have very important significance to the further research and large-scale commercial Application of synthesis SSZ-13 molecular sieves.
In order to solve the above technical problems, the present invention provides and a kind of synthesizing flat SSZ-13 molecular sieves with mixed templates
Method, characterized in that include the following steps：
Tetrahydrofuran is mixed with adamantane ammonium hydroxide and is used as mixed templates, sodium hydroxide is dissolved in deionization by step 1
Sodium hydroxide solution is formed in water, and mixed templates are added in sodium hydroxide solution and are sufficiently stirred to obtain mixed solution A；
Silicon source, silicon source are gradually added in the mixed solution A that step 1 obtains by step 2, are stirred 0.5 ~ 2 hour at room temperature
To uniform mixed gel；
The homogeneous gel mixture that step 2 obtains is transferred to crystallization in autoclave, room temperature cooling, solid phase production by step 3
Object is recovered by filtration, and is washed with deionized, dry, then in air 560 ° of С roastings to get to SSZ-13 molecular sieves.
Further, in above-mentioned steps one, the molar ratio of the tetrahydrofuran and adamantane ammonium hydroxide is 0.1 ~ 1.
Further, in above-mentioned steps one, the molar ratio of the sodium hydroxide and deionized water is 0.005 ~ 0.05.
Further, in above-mentioned steps two, the silicon source is one or both of white carbon, Ludox.
Further, in above-mentioned steps two, source of aluminium is one kind in sodium metaaluminate, boehmite and aluminium hydroxide
Or it is several.
Further, in above-mentioned steps two, silicon source is with SiO2Meter, silicon source is with Al2O3It counts, reacts former in the mixed solution A
Expect that mol ratio is：Al2O3：Water=0.001 ~ 0.1, Al2O3：Mixed templates=0.05 ~ 0.5, SiO2：Al2O3=10~50。
Further, in above-mentioned steps three, the autoclave is stainless steel, and is served as a contrast with polytetrafluoroethylene (PTFE)
In.
Further, in above-mentioned steps three, the crystallization condition is：Crystallization 1 ~ 8 day at a temperature of 150 ~ 280 ° of С.
Further, in above-mentioned steps three, the temperature of the drying is 80 ~ 150 ° of С.
Further, the pattern of the SSZ-13 molecular sieves of formation is that interlayer is flat.
The advantageous effect that the present invention is reached：It is closed using tetrahydrofuran and adamantane ammonium hydroxide mixed templates
At reducing the usage amount of adamantane ammonium hydroxide, reduce production cost.The SSZ-13 molecular sieves synthesized by the present invention have
The flat pattern of interlayer, and its solid phase yield is high, better crystallinity degree, the further research to synthesis SSZ-13 molecular sieves and big rule
The commercial Application of mould has very important significance.The building-up process has very in terms of reducing production cost and improving crystallinity
Good effect.
Description of the drawings
Fig. 1 is the XRD spectrum for the SSZ-13 molecular sieves that the embodiment of the present invention 1 obtains；
Fig. 2 is the SEM figures for the SSZ-13 Molecular Sieve Morphology structures that the embodiment of the present invention 2 obtains；
Fig. 3 is the SEM figures for the SSZ-13 Molecular Sieve Morphology structures that the embodiment of the present invention 3 obtains；
Fig. 4 is the SEM figures for the SSZ-13 Molecular Sieve Morphology structures that the embodiment of the present invention 5 obtains.
Specific implementation mode
The invention will be further described below in conjunction with the accompanying drawings.Following embodiment is only used for clearly illustrating the present invention
Technical solution, and not intended to limit the protection scope of the present invention.
Embodiment 1：
In the method that mixed templates synthesize flat SSZ-13 molecular sieves, steps are as follows：
Step 1：It weighs 5.12g amantadines ammonium hydroxide and 0.20g tetrahydrofurans is uniformly mixed；Weigh 0.21g sodium hydroxides
It is dissolved completely in 15ml deionized waters.Mixed templates are added in sodium hydroxide solution, 1h is stirred at room temperature and obtains
Mixed solution A.The molar ratio of tetrahydrofuran and adamantane ammonium hydroxide is 0.5
Step 2：Weigh 0.1g aluminium hydroxides（ Al2O3Content 96%）It is added in the mixed solution A that step 1 obtains, fully
Stirring is until being completely dissolved；Then 1.5g white carbons are weighed（SiO2 contents are more than 99%）It is added in solution, is stirred at room temperature
1h is sufficiently mixed to obtain homogeneous gel mixture.The proportioning of mixed gel is Al2O3：NaOH：SiO2：（Tetrahydrofuran+adamantane
Ammonium hydroxide）：H2O = 1：0.2 ：50 ：0.3：50.
Step 3：The homogeneous gel mixture that step 2 obtains is transferred to the stainless steel water with teflon lined
In thermal response kettle, in a static condition, crystallization 6 days at a temperature of 160 ° of С；Room temperature cools down, and solid product is recovered by filtration, and uses
Deionized water washing is multiple, is then dried overnight at 100 ° of С, and finally 560 ° of С roast 10h in Muffle furnace, finally obtain
SSZ-13 molecular sieves.The XRD spectrum of SSZ-13 molecular sieves as shown in Figure 1, it was demonstrated that synthesized SSZ-13 molecular sieves.
Embodiment 2：
In the method that mixed templates synthesize flat SSZ-13 molecular sieves, the basic step prepared is same as Example 1, no
Be：In step 1, the molar ratio of tetrahydrofuran and adamantane ammonium hydroxide becomes 0.1 from 0.5, as a result, it has been found that obtain
SSZ-13 molecular sieve crystallinities are preferable, and pattern is flat in interlayer.SEM phenograms as shown in Figure 2.
Embodiment 3：
In the method that mixed templates synthesize flat SSZ-13 molecular sieves, the basic step prepared is same as Example 1, no
Be：In step 1, the molar ratio of tetrahydrofuran and adamantane ammonium hydroxide becomes 1 from 0.5, as a result, it has been found that obtained SSZ-
13 molecular sieve crystallinities are poor, and crystal morphology is irregular, rough surface.SEM phenograms as shown in Figure 3.
Embodiment 4：
In the method that mixed templates synthesize flat SSZ-13 molecular sieves, the basic step prepared is same as Example 1, no
Be：In step 2, SiO2：Al2O3It is 50, becomes SiO2：Al2O3=30, SiO2：Al2O3=10, as a result, it has been found that with sial
The reduction of ratio has still obtained the high SSZ-13 molecular sieves of crystallinity.
Embodiment 5：
In the method that mixed templates synthesize flat SSZ-13 molecular sieves, the basic step prepared is same as Example 1, no
Be：In step 3, crystallization condition becomes 160 ° of С for 6 days 5 days from 160 ° of С, finally obtained SSZ-13 crystallization of molecular sieves
Degree is general, and part surface is coarse irregular.SEM phenograms as shown in Figure 4.
Embodiment 6：
In the method that mixed templates synthesize flat SSZ-13 molecular sieves, the basic step prepared is same as Example 1, no
Be：In step 3, crystallization condition becomes 180 ° of С for 6 days 5 days from 160 ° of С, finally obtained SSZ-13 crystallization of molecular sieves
Degree is high, and crystal morphology is good.
Embodiment 7：
In the method that mixed templates synthesize flat SSZ-13 molecular sieves, the basic step prepared is same as Example 1, no
Be：In step 3, crystallization condition becomes 150 ° of С for 6 days 6 days from 160 ° of С, as a result, it has been found that there are part amorphous states
SSZ-13 molecular sieves.
According to above-described embodiment 1 to 7 it is found that the mol ratio of tetrahydrofuran and adamantane ammonium hydroxide is to the SSZ- of synthesis
The crystallinity and pattern quality of 13 molecular sieves have an impact, can when the molar ratio of tetrahydrofuran and adamantane ammonium hydroxide is 0.5
To synthesize the preferable SS-13 molecular sieves of pattern, crystallinity, and regular appearance.The crystalline substance of crystallization temperature and crystallization time to synthesis
Bodily form looks and crystallinity all have an impact；It improves crystallization temperature and extends the synthesis that crystallization time is conducive to SSZ-13 molecular sieves.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates, characterized in that include the following steps：
Tetrahydrofuran is mixed with adamantane ammonium hydroxide and is used as mixed templates, sodium hydroxide is dissolved in deionization by step 1
Sodium hydroxide solution is formed in water, and mixed templates are added in sodium hydroxide solution and are sufficiently stirred to obtain mixed solution A；
Silicon source, silicon source are gradually added in the mixed solution A that step 1 obtains by step 2, are stirred 0.5 ~ 2 hour at room temperature
To uniform mixed gel；
The homogeneous gel mixture that step 2 obtains is transferred to crystallization in autoclave, room temperature cooling, solid phase production by step 3
Object is recovered by filtration, and is washed with deionized, dry, then in air 560 ° of С roastings to get to SSZ-13 molecular sieves.
2. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that in above-mentioned steps one, the molar ratio of the tetrahydrofuran and adamantane ammonium hydroxide is 0.1 ~ 1.
3. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that in above-mentioned steps one, the molar ratio of the sodium hydroxide and deionized water is 0.005 ~ 0.05.
4. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that in above-mentioned steps two, the silicon source is one or both of white carbon, Ludox.
5. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that in above-mentioned steps two, source of aluminium is one or more of sodium metaaluminate, boehmite and aluminium hydroxide.
6. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that in above-mentioned steps two, silicon source is with SiO2Meter, silicon source is with Al2O3It counts, reaction raw materials mol ratio is in the mixed solution A：
Al2O3：Water=0.001 ~ 0.1, Al2O3：Mixed templates=0.05 ~ 0.5, SiO2：Al2O3=10~50。
7. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that in above-mentioned steps three, the autoclave is stainless steel, and carries teflon lined.
8. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that in above-mentioned steps three, the crystallization condition is：Crystallization 1 ~ 8 day at a temperature of 150 ~ 280 ° of С.
9. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that in above-mentioned steps three, the temperature of the drying is 80 ~ 150 ° of С.
10. a kind of method synthesizing flat SSZ-13 molecular sieves with mixed templates according to claim 1, feature
It is that the pattern of the SSZ-13 molecular sieves of formation is that interlayer is flat.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665545A (en) * | 2019-02-14 | 2019-04-23 | 正大能源材料(大连)有限公司 | A kind of synthetic method of controllable appearance SSZ-13 molecular sieve |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830007A (en) * | 2017-03-17 | 2017-06-13 | 中触媒新材料股份有限公司 | With the molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106830007A (en) * | 2017-03-17 | 2017-06-13 | 中触媒新材料股份有限公司 | With the molecular sieve catalysts of multi-stage porous SSZ 13 and its synthetic method and application |
Non-Patent Citations (3)
| Title |
|---|
| QINGLING LIU ET AL.: "MnOx-CeO2 supported on Cu-SSZ-13: A novel SCR catalyst in a wide temperature range", 《APPLIED CATALYSIS A, GENERAL》 * |
| ZEBASTIAN BOHSTROM: "Preparation of high silica chabazite with controllable particle size", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665545A (en) * | 2019-02-14 | 2019-04-23 | 正大能源材料(大连)有限公司 | A kind of synthetic method of controllable appearance SSZ-13 molecular sieve |
| CN109665545B (en) * | 2019-02-14 | 2022-07-01 | 正大能源材料(大连)有限公司 | Synthesis method of morphology-controllable SSZ-13 molecular sieve |
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Effective date of registration: 20200827 Address after: 116036, No. 7, Ying Sheng Road, Ying Cheng Industrial Park, Ganjingzi District, Liaoning, Dalian Patentee after: CHIA TAI ENERGY MATERIALS (DALIAN) Co.,Ltd. Address before: 116036, No. 7, Ying Sheng Road, Ying Cheng Industrial Park, Ganjingzi District, Liaoning, Dalian Co-patentee before: Tianjin University Patentee before: CHIA TAI ENERGY MATERIALS (DALIAN) Co.,Ltd. |
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