CN104386706A - Method for synthesizing CHA-type molecular sieve by using zinc-amine complex as template agent - Google Patents
Method for synthesizing CHA-type molecular sieve by using zinc-amine complex as template agent Download PDFInfo
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- CN104386706A CN104386706A CN201410616666.XA CN201410616666A CN104386706A CN 104386706 A CN104386706 A CN 104386706A CN 201410616666 A CN201410616666 A CN 201410616666A CN 104386706 A CN104386706 A CN 104386706A
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- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention relates to a method for synthesizing a CHA-type molecular sieve by using a zinc-amine complex as a template agent. According to the method, sodium aluminate, organic amine, silica sol, sodium hydroxide and soluble zinc salt as raw materials are subjected to hydrothermal reaction. The method is characterized by comprising the steps of reacting a sodium aluminate aqueous solution and a soluble zinc salt aqueous solution added with tetraethylenepentamine, adding sodium hydroxide solids and silica sol, stirring for 3-5 hours, loading the mixture into a reactor and crystallizing for 2-8 days at a temperature of 130-160 DEG C; after the reaction is completed, sufficiently washing the reaction product with deionized water, drying for 14-16 hours in an oven of which the temperature is 70-95 DEG C, heating and carrying out heat exchange for 2-15 hours at 80-100 DEG C by virtue of 0.1-1mol/L ammonium nitrate and removing the template agent by calcining for 6-8 hours at 400-450 DEG C to obtain the final product. The CHA-type molecular sieve synthesized by the method has higher crystallinity; since the zinc-amine complex is adopted as the template agent instead of expensive amantadine template agent molecules, the production cost is greatly decreased, and the CHA-type molecular sieve is conducive to meeting the needs of industrial production and can be used as a catalyst.
Description
Technical field
The invention belongs to molecular sieve art, a kind of method of cheapness synthesis CHA type molecular sieve is provided.
Background technology
Molecular sieve is the one of porous material, because it has rule and uniform pore passage structure, good absorption property and select type, thus play a part more and more important in refining of petroleum, petrochemical complex and fine chemistry industry and daily-use chemical industry as main catalytic material, adsorption and separation material and ion-exchange material.Due to the needs in above-mentioned three large fields, the molecular sieve of current known synthetic has reached kind more than hundred, and from the diversity of component element and skeleton structure, still has very large development space.But really plant for plant-scale only LTA type, FAU type, MOR type, LTL type, MFI type, BEA type, MTW type, CHA type, FER type, AEL type and TON type etc. more than ten up to now.Wherein CHA type molecular sieve shows higher catalytic reaction activity and selectivity in the MTO reaction of methanol-to-olefins, is thus subject to extensive concern.
CHA type molecular sieve (SSZ-13 molecular sieve) has octatomic ring pore passage structure, having and in methanol to olefins reaction, show higher hydrothermal stability and thermostability and non-easy in inactivation compared with the SSZ-13 molecular sieve of high silica alumina ratio, is that people grind high focus.And the template being widely used in synthesis SSZ-13 molecular sieve is at present 1-amantadine TMAdaOH (N, N, N-trimethyl-1-1-adamantammoniumhydroxide).This organic molecule sieve series Preparation Method is complicated, expensive, makes it apply and is restricted.Within 2006, mentioned in the U.S. Patent No. 60/826.882 of application by people such as Zones, they are by adding toluene quaternary ammonium ion and TMAda
+positively charged ion can reduce TMAda significantly as the structure directing agent of reactant together
+cationic using dosage, but its synthesis cost is still higher.The people such as nearest Xiao Fengshou in Chinese patent CN101973562 B using copper-amine complex as template one-step synthesis Cu-SSZ-13 molecular sieve. in building-up process, copper-amine complex is template molecule, be again the direct sources of catalytic active component copper species.Although this method is avoided using expensive amantadine template, the ion-exchange capacity of product is poor, and cupric ion is difficult to removing, and be not easily converted into SSZ-13, therefore Application Areas is narrow.
Summary of the invention
The object of the present invention is to provide a kind of with the method for zinc amine complex for template synthesis CHA type molecular sieve.The method can provide one with zinc amine complex for template one step hydro thermal method synthesis SSZ-13 molecular sieve.
For achieving the above object, the present invention adopts following technical scheme:
The present invention with sodium metaaluminate, organic amine, silicon sol, sodium hydroxide and soluble zinc salt for raw material carries out hydro-thermal reaction, concrete steps are reacted at the sodium metaaluminate aqueous solution and the soluble Zn salt brine solution (the Zn-R zinc amine complex namely generated) adding organic amine, add sodium hydrate solid and silicon sol again, stirring loaded in reactor after 3-5 hour, crystallization 2 ~ 8 days at the temperature of 130 ~ 160 DEG C; After having reacted, reaction product deionized water is fully washed, dry 14-16 hour in 70-95 DEG C of baking oven, at 80-100 DEG C, add heat exchange 2 ~ 10h by 1mol/L ammonium nitrate and at 400-450 DEG C of roasting 6-8 hour, removing template, obtains final product.
The mol ratio of each reaction raw materials is: SiO
2: Al
2o
3: Na
2o: H
2o: Zn-R is 6.5 ~ 150: 1: 2 ~ 50: 200: 1.5 ~ 10.Described Zn-R is zinc amine complex, and wherein Zn is the zine ion of divalence, and R is the organic amine with zinc complexing.Described organic amine is tetraethylene pentamine.Soluble zinc salt is any one in zinc sulfate, zinc chloride, zinc nitrate and zinc acetate, and the mol ratio of Zn, R is 1: 1.
The invention provides a kind of new structure directing agent to synthesize SSZ-13 molecular sieve, namely zinc and tetraethylene pentamine title complex are as structure directing agent.This directed agents is cheap, and minimizing technology is easy, has very large prospects for commercial application.The CHA type molecular sieve crystallinity of the present invention's synthesis is higher, instead of expensive amantadine template molecule, greatly reduce production cost, be conducive to meeting industrial demand, use as catalyzer using zinc amine complex as template.
Accompanying drawing explanation
Fig. 1: the XRD spectra of embodiment 1 product; Fig. 2: the SEM picture of embodiment 1 product.
Fig. 3: the XRD spectra of embodiment 2 product; Fig. 4: the XRD spectra of embodiment 3 product.
Fig. 5: the XRD spectra of embodiment 4 product; Fig. 6: the XRD spectra of embodiment 5 product.
Fig. 7: the XRD spectra of embodiment 6 product.
Embodiment
The present invention is described in further detail by the following examples, and this does not limit the scope of the invention.
The experimental technique of unreceipted actual conditions in embodiment, usually conveniently condition and the condition described in handbook, or according to the condition that manufacturer advises.Material used, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1:CHA sample
First 1.134 grams of sodium metaaluminates are dissolved in 6.3 grams of deionized waters and obtain solution A, 2.875 grams of Zinc vitriols are dissolved in and drip tetraethylene pentamine 1.893 grams after 6.3 grams of deionized water for stirring dissolve 0.5 hour and obtain solution B, again solution B is dropwise added in solution A, after fully stirring 0.5 hour, add sodium hydrate solid 1.05 grams and silicon sol 7.5 grams again, abundant stirring loaded in reactor after 3 hours, crystallization 6 days at the temperature of 150 DEG C; After having reacted, reaction product deionized water is fully washed, and in 75 DEG C of baking ovens dry 14 hours, at 90 DEG C, add heat exchange 6h by 1mol/L ammonium nitrate and in 450 DEG C of roastings, 6 hours removing template, obtain final product; The mol ratio of each reaction raw materials is: SiO
2: Al
2o
3: Na
2o: H
2o: Zn-R is 10: 1: 2.5: 200: 2.
Accompanying drawing 1 is the XRD characterization result of product, can find out that product is CHA structure, and have higher degree of crystallinity.
Accompanying drawing 2 is the stereoscan photograph of product, can find out that the particle diameter of product is approximately the cubic system of about 5nm.
The preparation of embodiment 2:CHA sample
Feed intake in experiment, step, treatment process be identical with embodiment 1, just crystallization condition be crystallization 5 days at 140 DEG C, and taking-up reactor, filtering and washing, obtains product 2.
Accompanying drawing 3 is the XRD characterization result of product, can find out that product is CHA structure, and spectrogram baseline is relatively more flat illustrates that product has higher degree of crystallinity.
The preparation of embodiment 3:CHA sample
Feed intake in experiment, step, treatment process be identical with embodiment 2, just crystallization time is extended to 8 days, take out reactor, filtering and washing, obtain product 3. in 450 DEG C of roastings, 6 hours removing template
Accompanying drawing 4 is the XRD characterization result of product, and can find out that product is CHA structure, the degree of crystallinity of product is higher.
The preparation of embodiment 4:CHA sample
Feed intake in experiment, step, treatment process be identical with embodiment 1, just crystallization condition be crystallization 6 days at 160 DEG C, takes out reactor, filtering and washing, within 6 hours, removes template obtain product 3 450 DEG C of roastings.
Accompanying drawing 5 is the XRD characterization result of product, can find out that product is CHA structure, and spectrogram baseline is relatively more flat illustrates that product has higher degree of crystallinity.
The preparation of embodiment 5:CHA sample
The consumption of Zinc vitriol is 4.313 grams, and the consumption of tetraethylene pentamine is 2.840 grams, and feed intake middle Zn-R and Al
2o
3mol ratio be 3.Other in experiment feeds intake, step, treatment process are identical with embodiment 1.Products obtained therefrom is designated as product 5, and its XRD figure is as Fig. 6.The baseline of the XRD spectra of product 5 is more flat, illustrates that the degree of crystallinity of product is higher.
The preparation of embodiment 6:CHA sample
The consumption of Zinc vitriol is 5.750 grams, and the consumption of tetraethylene pentamine is 3.786 grams, and feed intake middle Zn-R and Al
2o
3mol ratio be 4.Other in experiment feeds intake, step, treatment process are identical with embodiment 1.Products obtained therefrom is designated as product 6, and its XRD figure is as Fig. 7.The baseline of the XRD spectra of product 5 is more flat, illustrates that the degree of crystallinity of product is higher.
Claims (5)
1. one kind with the method for zinc amine complex for template synthesis CHA type molecular sieve, it is for raw material carries out hydro-thermal reaction with sodium metaaluminate, organic amine, silicon sol, sodium hydroxide and soluble zinc salt, it is characterized in that the sodium metaaluminate aqueous solution and the soluble zinc salt reactant aqueous solution adding organic amine, add sodium hydrate solid and silicon sol again, stirring loaded in reactor after 3-5 hour, crystallization 2 ~ 8 days at the temperature of 130 ~ 160 DEG C; After having reacted, reaction product deionized water is fully washed, dry 14-16 hour in 70-95 DEG C of baking oven, at 80-100 DEG C, add heat exchange 2 ~ 15h by 0.1 ~ 1mol/L ammonium nitrate and at 400-450 DEG C of roasting 6-8 hour, removing template, obtains final product;
The mol ratio of described each reaction raw materials is: SiO
2: Al
2o
3: Na
2o: H
2o: Zn-R is 6.5 ~ 150: 1: 2 ~ 50: 200: 1.5 ~ 10; Described Zn-R is zinc amine complex, and wherein Zn is the zine ion of divalence, and R is the organic amine with zinc complexing; The mol ratio of Zn, R is 1: 1.
2. method according to claim 1, is characterized in that the mol ratio of described each reaction raw materials is: SiO
2: Al
2o
3: Na
2o: H
2o: Zn-R is 10: 1: 2.5: 200: 2.
3. method according to claim 1, is characterized in that described organic amine is tetraethylene pentamine.
4. method according to claim 1, is characterized in that described soluble zinc salt is any one in zinc sulfate, zinc nitrate, zinc chloride or zinc acetate.
5. method according to claim 1, is characterized in that Zn-R and Al in described reaction raw materials
2o
3mol ratio is: 1.5-10: 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109110780A (en) * | 2017-06-22 | 2019-01-01 | 中国科学院宁波材料技术与工程研究所 | A kind of method of Vacuum-assisted method Cu-SSZ-13 molecular sieve |
| JP2019089666A (en) * | 2017-11-13 | 2019-06-13 | 国立大学法人 東京大学 | Method for producing zeolite, chabazite-type zeolite, and ion exchanger comprising the same |
| CN113149027A (en) * | 2021-05-08 | 2021-07-23 | 浙江大学 | Method for synthesizing Co-SSZ-13 zeolite molecular sieve by one step by using cobalt-amine complex as template agent |
| WO2022214655A1 (en) | 2021-04-09 | 2022-10-13 | Umicore Ag & Co. Kg | One-pot synthesis of transition metal-promoted chabazites |
| CN115920955A (en) * | 2022-12-22 | 2023-04-07 | 山东泓泰恒瑞新材料有限公司 | Cu-Zn-SSZ-13 molecular sieve composite catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101242887A (en) * | 2005-06-23 | 2008-08-13 | 切夫里昂美国公司 | Molecular sieve SSZ-56 composition and synthesis thereof |
| CN103601211A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Synthesis method of molecular sieve SSZ-13 |
| WO2014090698A1 (en) * | 2012-12-12 | 2014-06-19 | Haldor Topsøe A/S | One-pot method for the synthesis of cu-ssz-13, the compound obtained by the method and use thereof |
| CN103930370A (en) * | 2011-09-16 | 2014-07-16 | 巴斯夫欧洲公司 | Process for the production of a core/shell zeolitic material having a CHA framework structure |
-
2014
- 2014-11-04 CN CN201410616666.XA patent/CN104386706B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101242887A (en) * | 2005-06-23 | 2008-08-13 | 切夫里昂美国公司 | Molecular sieve SSZ-56 composition and synthesis thereof |
| CN103930370A (en) * | 2011-09-16 | 2014-07-16 | 巴斯夫欧洲公司 | Process for the production of a core/shell zeolitic material having a CHA framework structure |
| WO2014090698A1 (en) * | 2012-12-12 | 2014-06-19 | Haldor Topsøe A/S | One-pot method for the synthesis of cu-ssz-13, the compound obtained by the method and use thereof |
| CN103601211A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Synthesis method of molecular sieve SSZ-13 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109110780A (en) * | 2017-06-22 | 2019-01-01 | 中国科学院宁波材料技术与工程研究所 | A kind of method of Vacuum-assisted method Cu-SSZ-13 molecular sieve |
| JP2019089666A (en) * | 2017-11-13 | 2019-06-13 | 国立大学法人 東京大学 | Method for producing zeolite, chabazite-type zeolite, and ion exchanger comprising the same |
| JP7131753B2 (en) | 2017-11-13 | 2022-09-06 | 国立大学法人 東京大学 | Method for producing zeolite, chabazite-type zeolite, and ion exchanger comprising the same |
| WO2022214655A1 (en) | 2021-04-09 | 2022-10-13 | Umicore Ag & Co. Kg | One-pot synthesis of transition metal-promoted chabazites |
| CN113149027A (en) * | 2021-05-08 | 2021-07-23 | 浙江大学 | Method for synthesizing Co-SSZ-13 zeolite molecular sieve by one step by using cobalt-amine complex as template agent |
| CN115920955A (en) * | 2022-12-22 | 2023-04-07 | 山东泓泰恒瑞新材料有限公司 | Cu-Zn-SSZ-13 molecular sieve composite catalyst and preparation method thereof |
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