CN104386706B - With the method that zinc amine complex synthesizes CHA type molecular sieve for template - Google Patents
With the method that zinc amine complex synthesizes CHA type molecular sieve for template Download PDFInfo
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- CN104386706B CN104386706B CN201410616666.XA CN201410616666A CN104386706B CN 104386706 B CN104386706 B CN 104386706B CN 201410616666 A CN201410616666 A CN 201410616666A CN 104386706 B CN104386706 B CN 104386706B
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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
- C01B39/04—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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- 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
Abstract
The present invention relates to the method synthesizing CHA type molecular sieve for template with zinc amine complex.It is to carry out hydro-thermal reaction with sodium metaaluminate, organic amine, Ludox, sodium hydroxide and soluble zinc salt for raw material, it is characterized in that sodium metaaluminate aqueous solution and the soluble zinc salt reactant aqueous solution being added with TEPA, add sodium hydrate solid and Ludox, load after stirring 3-5 hour in reactor, crystallization 2～8 days at the temperature of 130～160 DEG C；After having reacted, product deionized water is fully washed, dries 14-16 hour in 70-95 DEG C of baking oven, at 80-100 DEG C, add heat exchange 2～15h and 400-450 DEG C of roasting 6-8 hour by 0.1～1mol/L ammonium nitrate, remove template, obtain end product.The CHA type molecular sieve crystallinity of present invention synthesis is higher, instead of the amantadine template molecule of costliness using zinc amine complex as template, greatly reduces production cost, be conducive to meeting industrial demand, uses as catalyst.
Description
Technical field
The invention belongs to molecular sieve art, it is provided that a kind of method of cheap synthesis CHA type molecular sieve.
Background technology
Molecular sieve is the one of porous material, the uniform pore passage structure because it has a rule, good absorption property and select type, thus playing more and more important effect as main catalysis material, adsorption and separation material and ion exchange material in PETROLEUM PROCESSING, petrochemical industry and fine chemistry industry and daily-use chemical industry.Due to the needs in above-mentioned three big fields, the molecular sieve being currently known synthetic has reached kind more than hundred, and from the multiformity of component element Yu framing structure, still has very big development space.But plant-scale only LTA type, FAU type, MOR type, LTL type, MFI type, BEA type, MTW type, CHA type, FER type, AEL type and the TON types etc. more than ten that really have been used for up to now are planted.Wherein CHA type molecular sieve shows higher catalytic reaction activity and selectivity in the MTO of methanol-to-olefins reacts, thus receives significant attention.
CHA type molecular sieve (SSZ-13 molecular sieve) has octatomic ring pore passage structure, the SSZ-13 molecular sieve with relatively high silica alumina ratio shows higher hydrothermal stability and heat stability and non-easy in inactivation in methanol to olefins reaction, is that people grind high focus.And the template being now widely used in synthesis SSZ-13 molecular sieve is 1-amantadine TMAdaOH (N, N, N-trimethyl-1-1-adamantammoniumhydroxide).This organic molecule sieve series Preparation Method is complicated, expensive so that it is application is restricted.Within 2006, being mentioned in the U.S. Patent No. 60/826.882 of application by Zones et al., they are by adding toluene quaternary ammonium ion and TMAda+Cation can reduce TMAda significantly together as the structure directing agent of reactant+Cationic using dosage, but its synthesis cost is still higher.Nearest Xiao Fengshou et al. in Chinese patent CN101973562B 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 the method is avoided using expensive amantadine template, but the ion-exchange capacity of product is poor, and copper ion is difficult to remove, and is not readily converted into SSZ-13, and therefore application is narrow.
Summary of the invention
It is an object of the invention to provide a kind of method synthesizing CHA type molecular sieve for template with zinc amine complex.The method can provide a kind of and synthesize SSZ-13 molecular sieve with zinc amine complex for template one step hydro thermal method.
For achieving the above object, the present invention adopts the following technical scheme that
The present invention carries out hydro-thermal reaction with sodium metaaluminate, organic amine, Ludox, sodium hydroxide and soluble zinc salt for raw material, comprise the concrete steps that and sodium metaaluminate aqueous solution and the soluble Zn saline solution (the Zn-R zinc amine complex namely generated) adding organic amine are reacted, add sodium hydrate solid and Ludox, load after stirring 3-5 hour in reactor, crystallization 2～8 days at the temperature of 130～160 DEG C；After having reacted, 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 and 400-450 DEG C of roasting 6-8 hour by 1mol/L ammonium nitrate, remove template, obtain end product.
The mol ratio of each reaction raw materials is: SiO2∶Al2O3∶Na2O∶H2O: 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 zinc ion of bivalence, and R is and the organic amine of zinc complexation.Described organic amine is TEPA.Soluble zinc salt is any one in zinc sulfate, zinc chloride, zinc nitrate and zinc acetate, Zn, and the mol ratio of R is 1: 1.
The invention provides a kind of new structure directing agent to synthesize SSZ-13 molecular sieve, namely zinc and TEPA coordination compound are as structure directing agent.This directed agents is cheap, and minimizing technology is easy, has very big prospects for commercial application.The CHA type molecular sieve crystallinity of present invention synthesis is higher, instead of the amantadine template molecule of costliness using zinc amine complex as template, greatly reduces production cost, be conducive to meeting industrial demand, uses as catalyst.
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.
Detailed description of the invention
The present invention is described in further detail by the following examples, and this is not limiting as protection scope of the present invention.
The experimental technique of unreceipted actual conditions in embodiment, the generally conventionally condition described in condition and handbook, or according to manufacturer it is proposed that condition.Used material, reagent etc., if no special instructions, all commercially obtain.
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 dropping TEPA 1.893 grams after 6.3 grams of deionized water for stirring are dissolved 0.5 hour and obtain solution B, again solution B is added dropwise in solution A, after being sufficiently stirred for 0.5 hour, add sodium hydrate solid 1.05 grams and Ludox 7.5 grams, load after being sufficiently stirred for 3 hours in reactor, crystallization 6 days at the temperature of 150 DEG C；After having reacted, product deionized water is fully washed, and dry 14 hours in 75 DEG C of baking ovens, at 90 DEG C, add heat exchange 6h by 1mol/L ammonium nitrate and within 6 hours, remove template 450 DEG C of roastings, obtaining end product；The mol ratio of each reaction raw materials is: SiO2∶Al2O3∶Na2O∶H2O: Zn-R is 10: 1: 2.5: 200: 2.
Accompanying drawing 1 is the XRD characterization result of product, it can be seen that product is CHA structure, and has higher degree of crystallinity.
Accompanying drawing 2 is the stereoscan photograph of product, it can be seen that the particle diameter of product is approximately the cubic crystal of about 5nm.
The preparation of embodiment 2:CHA sample
Experiment feeds intake, step, processing method and embodiment 1 identical, simply crystallization condition be crystallization 5 days at 140 DEG C, taking-up reactor, and filtering and washing obtains product 2.
Accompanying drawing 3 is the XRD characterization result of product, it can be seen 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
Experiment feeds intake, step, processing method and embodiment 2 identical, simply crystallization time is extended to 8 days, takes out reactor, filtering and washing, within 6 hours, remove template 450 DEG C of roastings and obtain product 3.
Accompanying drawing 4 is the XRD characterization result of product, it can be seen that product is CHA structure, and the degree of crystallinity of product is higher.
The preparation of embodiment 4:CHA sample
Experiment feeds intake, step, processing method and embodiment 1 identical, simply crystallization condition be crystallization 6 days at 160 DEG C, takes out reactor, filtering and washing, obtains product 3 in 6 hours removing template of 450 DEG C of roastings.
Accompanying drawing 5 is the XRD characterization result of product, it can be seen 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 TEPA is 2.840 grams, and feed intake middle Zn-R and Al2O3Mol ratio be 3.Other in experiment feeds intake, step, processing method and embodiment 1 identical.Products obtained therefrom is designated as product 5, its XRD figure such 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 TEPA is 3.786 grams, and feed intake middle Zn-R and Al2O3Mol ratio be 4.Other in experiment feeds intake, step, processing method and embodiment 1 identical.Products obtained therefrom is designated as product 6, its XRD figure such 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 (3)
1. the method synthesizing CHA type molecular sieve for template with zinc amine complex, it is to carry out hydro-thermal reaction with sodium metaaluminate, organic amine, Ludox, sodium hydroxide and soluble zinc salt for raw material, it is characterized in that sodium metaaluminate aqueous solution and the soluble zinc salt reactant aqueous solution adding organic amine, add sodium hydrate solid and Ludox, load after stirring 3-5 hour in reactor, crystallization 2～8 days at the temperature of 130～160 DEG C；After having reacted, product deionized water is fully washed, dries 14-16 hour in 70-95 DEG C of baking oven, at 80-100 DEG C, add heat exchange 2～15h and 400-450 DEG C of roasting 6-8 hour by 0.1～1mol/L ammonium nitrate, remove template, obtain end product；
The mol ratio of described each reaction raw materials is: SiO2∶Al2O3∶Na2O∶H2O: 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 zinc ion of bivalence, and R is and the organic amine of zinc complexation；The mol ratio of Zn, R is 1: 1；
Described organic amine is TEPA.
2. method according to claim 1, it is characterised in that the mol ratio of described each reaction raw materials is: SiO2∶Al2O3∶Na2O∶H2O: Zn-R is 10: 1: 2.5: 200: 2.
3. method according to claim 1, it is characterised in that described soluble zinc salt is any one in zinc sulfate, zinc nitrate, zinc chloride or zinc acetate.
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| 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 |
| 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 |
| CN117120374A (en) | 2021-04-09 | 2023-11-24 | 优美科股份公司及两合公司 | One-pot synthesis of transition metal promoted chabazite |
| 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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| ZA200800650B (en) * | 2005-06-23 | 2009-04-29 | Chevron Usa Inc | Molecular sieve SSZ-56 composition of matter 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 |
| CN104812469B (en) * | 2012-12-12 | 2017-05-03 | 托普索公司 | One-pot method for the synthesis of cu-ssz-13, the compound obtained by the method and use thereof |
| CN103601211B (en) * | 2013-12-04 | 2015-07-22 | 北京化工大学 | Synthesis method of molecular sieve SSZ-13 |
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