CN113582199A - Method for synthesizing chabazite by seed crystal guiding method and improving utilization rate of raw materials - Google Patents
Method for synthesizing chabazite by seed crystal guiding method and improving utilization rate of raw materials Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 50
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 title claims abstract description 45
- 239000013078 crystal Substances 0.000 title claims abstract description 36
- 239000002994 raw material Substances 0.000 title claims abstract description 27
- 229910052676 chabazite Inorganic materials 0.000 title claims description 33
- 230000002194 synthesizing effect Effects 0.000 title claims description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- 239000012452 mother liquor Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 11
- 239000010457 zeolite Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 102
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 229910001868 water Inorganic materials 0.000 claims description 28
- 229910052681 coesite Inorganic materials 0.000 claims description 24
- 229910052906 cristobalite Inorganic materials 0.000 claims description 24
- 229910052682 stishovite Inorganic materials 0.000 claims description 24
- 229910052905 tridymite Inorganic materials 0.000 claims description 24
- 239000000017 hydrogel Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 46
- 239000000126 substance Substances 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 229960003805 amantadine Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a synthesis method of a zeolite molecular sieve with a chabazite structure, which comprises the following steps: the zeolite molecular sieve with chabazite structure is prepared by a direct hydrothermal synthesis method through a seed crystal guiding method under the condition of not adding an organic template agent, and a synthesis mother liquor is recycled to be used as a raw material for next batch synthesis. The method does not use an organic template machine with high price, and simultaneously avoids high energy consumption and environmental pollution caused by removing the template agent by organic wastewater treatment and high-temperature roasting in the later period. In addition, the discharge of mother liquor is reduced or zero discharge of the mother liquor is realized, the comprehensive yield is improved, and the influence on the environment is reduced. Due to the characteristics of economy and environmental protection, the method has wide application prospect in the aspect of industrial production.
Description
Technical Field
The invention belongs to the field of zeolite molecular sieve preparation, and particularly relates to a method for synthesizing a zeolite molecular sieve with a chabazite structure.
Technical Field
The crystal structure of the chabazite molecular sieve is formed by compounding two constituent units of double six rings and a CHA cage, the constituent units are mutually cross-linked to form a three-dimensional net structure, the net structure has uniform pore passages, and the size of pores can reach 0.37 nm.
Chabazite material for catalyzing Methanol To Olefin (MTO), catalyzing NOx in automobile exhaust and separating N2/CO2And the like, but the industrial application of the complex template agent is limited due to the reasons that the common template agent for synthesizing the complex template agent is expensive in amantadine, the benzyl trimethyl ammonium template agent is high in toxicity, the complex template agent synthesized by copper and tetraethylenepentamine is Cu-SSZ-13, the ion exchange performance of the complex template agent is poor, and the like. In addition, chabazite molecular sievesThe catalyst is easy to coke in the catalytic application of methanol to olefin, leads to rapid deactivation, and also has serious restriction in the industrial application of MTO reaction. Particularly, as the national requirements on the control of automobile exhaust emission become stricter, the six national standards are implemented, and chabazite is more and more regarded as a new-generation SCR catalyst carrier. Based on the existing synthesis and application status of the molecular sieve. The method seeks a green low-cost synthesis route of the chabazite molecular sieve, and has very important theoretical significance and application value in exploring a synthesis method for improving the coking resistance, namely the catalytic performance of the chabazite molecular sieve.
International patent publication Nos. WO03/078324A1 and WO2005/063622A2 disclose another synthesis method for synthesizing chabazite with a high silica-alumina ratio, which is greater than 100. In addition, the fluoride is added in the formula, and the fluoride is difficult to produce and operate due to toxicity and strong corrosivity.
Chinese patent CN102442679B (2013) discloses a synthetic method of chabazite, and discloses chabazite synthesized by a seed crystal guiding method, without using a template and without using a fluoride. The raw material Si/Al ratio of the method is 5.2-32.0, but the product Si/Al ratio is not disclosed. The method requires more than 5-25 wt% of chabazite product to be added to the raw material as seed crystal to obtain larger amount of product.
Disclosure of Invention
The invention provides a method for synthesizing a zeolite molecular sieve with a chabazite structure, which is characterized in that an organic template agent-free synthesis route is adopted, and in the reaction for synthesizing the chabazite under the hydrothermal condition, no organic template agent is added, and chabazite seed crystals are added into a formula containing a silicon source compound, an aluminum source compound and an inorganic base, so that an aluminosilicate zeolite molecular sieve product with the chabazite structure is obtained. Furthermore, because more alkali is used in the synthesis formula, more silicon and aluminum compounds are dissolved in the mother liquor obtained by separating the synthesized product from the product, and therefore, the mother liquor can be recycled as part of raw materials of the next batch. And supplementing new raw materials to a proper concentration, and then carrying out the hydrothermal synthesis of the next batch. The mother liquor is recycled, the comprehensive yield is improved, the waste water discharge is reduced, and the raw material cost and the environmental cost are reduced. In addition, the method of the invention can shorten the time for synthesizing the chabazite and improve the production efficiency.
Specifically, the invention provides a method for synthesizing chabazite by a seed crystal guiding method and improving the utilization rate of raw materials, which comprises the following steps:
(1) preparing water, sodium hydroxide and potassium hydroxide into alkaline solution;
(2) dissolving an aluminum source compound in an alkaline solution at room temperature, slowly adding a silicon source compound at room temperature, and continuously stirring to obtain uniformly mixed hydrogel;
(3) adding a small amount of seed crystals into the hydrogel, and continuously stirring the mixture evenly at room temperature;
(4) sealing the mixture in a suitable container, and performing hydrothermal crystallization;
(5) separating and washing to obtain the aluminosilicate zeolite molecular sieve with chabazite structure;
(6) and (3) analyzing the concentration of sodium hydroxide, potassium hydroxide, silicon compounds (calculated by silicon dioxide) and aluminum compounds (calculated by aluminum oxide) in the mother liquor obtained by separation in the step (5), then returning to the step (1), sequentially adding a proper amount of water, sodium hydroxide, potassium hydroxide, aluminum compounds and silicon source compounds, then performing hydrothermal crystallization according to the steps (3) to (5) to obtain a chabazite product and recovering the product, wherein the mother liquor can be continuously recycled according to the method.
In the method of the invention, the silicon source compound is: one or more of silica sol and white carbon black; the aluminum source compound is one or more of sodium metaaluminate and aluminum nitrate.
In the method, the seed crystal is an SSZ-13 molecular sieve.
In the method of the present invention, the amount of the SSZ-13 molecular sieve seed crystals charged is 3% or less of the total amount of Si elements charged.
In the method of the invention, the molar ratio of each component in the reaction mixture is as follows: m2O：SiO2＝0.50～0.55：1，SiO2：Al2O3＝20～40：1，H2O：SiO2＝10～40：1，Wherein M is an alkali metal (Na, K).
In the method, the ratio of NaOH/(NaOH + KOH) is 0.8-0, and the dosage of KOH is not 0.
In the method, the crystallization temperature is 110-150 ℃, and the crystallization time is 1-2 days.
In the method, the silica-alumina ratio of the obtained molecular sieve product with the chabazite structure is greatly lower than that of the fed materials.
The invention has the beneficial effects that:
the method of the invention does not use organic template agent, reduces the cost of raw materials, and avoids the operation of removing the template agent in the post-treatment stage.
The method provided by the invention has the advantages that the mother liquor is recycled, the comprehensive yield is improved, the waste water discharge is reduced, and the raw material cost and the environmental cost are reduced.
According to the method, the seed crystal is added as the guiding agent, so that the time for synthesizing the molecular sieve is shortened.
Drawings
FIG. 1 is a schematic flow diagram of a zeolite molecular sieve of synthetic chabazite structure according to an embodiment of the present invention.
FIG. 2 is an electron micrograph of a product according to example 1 of the present invention.
FIG. 3 is a powder X-ray diffraction pattern of the products of examples 1-3 of the present invention.
FIG. 4 is a powder X-ray diffraction pattern of the products of examples 4-6 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar modules or modules having the same or similar functionality throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description herein, references to the description of "one embodiment," "another embodiment," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
The invention provides a method for synthesizing a zeolite molecular sieve with a chabazite structure, which is characterized in that the method is a synthetic route without an organic template agent, and the aluminosilicate zeolite molecular sieve with the chabazite structure is obtained by adding chabazite seed crystals and carrying out hydrothermal synthesis. The flow of the specific method is shown in fig. 1.
Firstly, preparing water, sodium hydroxide and potassium hydroxide into an alkaline solution → dissolving an aluminum source compound in the alkaline solution at room temperature → then slowly adding a silicon source compound at room temperature, stirring to obtain uniformly mixed hydrogel → adding a small amount of seed crystals into the hydrogel, continuously stirring uniformly at room temperature → sealing the mixture in a proper container, carrying out hydrothermal crystallization to obtain a product, carrying out product separation → separating to obtain a mother solution, returning to the step (1), sequentially adding a proper amount of water, sodium hydroxide, potassium hydroxide, the aluminum source compound and the silicon source compound, and recycling the hydrothermal crystallization and product recovery again, wherein the mother solution can be recycled by the method.
Therefore, the preparation method of the process does not use an organic template agent, reduces the cost of raw materials, and avoids the operation of removing the template agent in a post-treatment stage. The key point is that the mother liquor is recycled, the comprehensive yield is improved, the waste water discharge is reduced, and the raw material cost and the environmental cost are reduced.
Example 1:
5.89 g of sodium hydroxide and 3.51 g of potassium hydroxide were dissolved in 36.00 g of pure water at room temperature, and 1.64 g of sodium metaaluminate was added and dissolved with stirring. 30.00 g of 40% silica sol was added dropwise and stirred at room temperature for 0.5 hour. 0.60 g of seed crystal was added and stirred at room temperature to obtain a hydrogel.
The molar ratio of each raw material compound component in the hydrogel is calculated according to the corresponding oxide as follows:
M2O/SiO20.53, M represents the sum of Na and K, wherein NaOH/(NaOH + KOH) ═ 0.75.
SiO2/Al2O3＝20
H2O/SiO2＝15
The weight ratio of the seed crystal to the charged silica was 3%.
The hydrogel is transferred into a stainless steel kettle lined with a polytetrafluoroethylene lining for sealing, and hydrothermal crystallization is carried out for 1 day at 130 ℃. And after crystallization is finished, taking out the reaction kettle, naturally cooling, filtering and recovering the mother liquor. Washing the filter cake twice with a large amount of clear water, and drying to obtain the product.
The SEM micrograph of the product is shown in figure 2, and the product is a walnut-shaped particle with the diameter of 1-2 microns.
The XRD powder diffraction pattern of the product is shown in figure 3, and the product is known to have a chabazite crystal structure.
Chemical analysis shows that the chemical composition of the product is [ Na ]0.63K0.36|[Al1Si5.45O12.90]. The co-recovered product had a dry weight of 8.5 g, and the yield was about 95% based on the charged aluminum element and about 52% based on the charged silicon element.
Example 2:
the mother liquor recovered in example 1 was freed of losses during the recovery by filtration to give 60.0 g, which contained 4.78 g of NaOH, 2.76 g of KOH, 5.11 g of SiO by chemical analysis2And 47.72 g of water, the Al content is lower than the detection limit.
To this, 1.10 g of sodium hydroxide and 0.75 g of potassium hydroxide were added in this order, and dissolved by stirring. 1.64 g of sodium metaaluminate, supplemented with 17.2 g of 40% silica sol, are added. Stirring was continued at room temperature for 0.5 h. 0.60 g of seed crystal was added and stirred at room temperature to obtain a hydrogel.
The molar ratio of each raw material compound component in the hydrogel is calculated according to the corresponding oxide as follows:
M2O/SiO20.53, M represents the sum of Na and K, wherein NaOH/(NaOH + KOH) ═ 0.75.
SiO2/Al2O3＝20
H2O/SiO2＝16
The weight ratio of the seed crystal to the charged silica was 3%.
The hydrogel is transferred into a stainless steel kettle lined with a polytetrafluoroethylene lining for sealing, and hydrothermal crystallization is carried out for 2 days at the temperature of 110 ℃. And after crystallization is finished, taking out the reaction kettle, naturally cooling, filtering and recovering the mother liquor. Washing the filter cake twice with a large amount of clear water, and drying to obtain the product.
The XRD powder diffraction pattern of the product is shown in figure 3, and the product is known to have a chabazite crystal structure.
Chemical analysis shows that the chemical composition of the product is | Na0.65K0.33|[Al1Si5.12O12.24]. The co-recovered product had a dry weight of 8.3 g, and the yield was about 93% by the amount of charged aluminum element and about 50% by the amount of charged silicon element.
Example 3:
the mother liquor recovered in example 2 was subjected to filtration recovery to remove the loss during recovery to obtain 60.0 g, which contained 4.50 g of NaOH, 2.82 g of KOH, and 5.30 g of SiO in chemical analysis2With 47.38 g of water, Al content according to NaAlO2Calculated as 0.07 grams.
To this, 1.40 g of sodium hydroxide and 0.70 g of potassium hydroxide were added in this order, and dissolved by stirring. 1.57 g of sodium metaaluminate, supplemented with 16.75 g of 40% silica sol, are added. Stirring was continued at room temperature for 0.5 h. 0.60 g of seed crystal was added and stirred at room temperature to obtain a hydrogel.
The molar ratio of each raw material compound component in the hydrogel is calculated according to the corresponding oxide as follows:
M2O/SiO20.53, M represents the sum of Na and K, wherein NaOH/(NaOH + KOH) ═ 0.75.
SiO2/Al2O3＝20
H2O/SiO2＝16
The weight ratio of the seed crystal to the charged silica was 3%.
The hydrogel is transferred into a stainless steel kettle lined with a polytetrafluoroethylene lining for sealing, and hydrothermal crystallization is carried out for 2 days at 150 ℃. And after crystallization is finished, taking out the reaction kettle, naturally cooling, filtering and recovering the mother liquor. Washing the filter cake twice with a large amount of clear water, and drying to obtain the product.
The XRD powder diffraction pattern of the product is shown in figure 3, and the product is known to have a chabazite crystal structure.
Chemical analysis shows that the chemical composition of the product is | Na0.68K0.30|[Al1Si5.80O13.60]. The co-recovered product had a dry weight of 8.7 g, and the yield was about 97% based on the charged aluminum element and about 55% based on the charged silicon element.
Example 4
2.0 g of sodium hydroxide and 10.00 g of potassium hydroxide were dissolved in 135.00 g of pure water at room temperature. 0.820 g of sodium metaaluminate is added and stirred to dissolve. 12.00 g of white carbon black was added in several portions and stirred at room temperature for 0.5 hour. 0.60 g of seed crystal was added and stirred at room temperature.
The molar ratio of each raw material compound component in the prepared hydrogel is calculated according to the corresponding oxide as follows:
M2O/SiO20.52, M represents the sum of Na and K, wherein NaOH/(NaOH + KOH) is 0.25.
SiO2/Al2O3＝40
H2O/SiO2＝37.5
The weight ratio of the seed crystal to the charged silica was 3%.
The hydrogel is transferred into a stainless steel reaction kettle lined with a polytetrafluoroethylene lining for sealing, and hydrothermal crystallization is carried out for 1 day at 130 ℃. And after crystallization is finished, taking out the reaction kettle, naturally cooling, and filtering to separate the mother liquor and the solid product. Washing the product with water and drying.
The XRD powder diffraction pattern of the product is shown in figure 4, and the product can be known to have the chabazite crystal structure.
Chemical analysis shows that the chemical composition of the product is | Na0.13K0.85|[Al1Si12.20O26.40]. The co-recovered product had a dry weight of 7.8 g, and the yield was about 90% by the amount of charged aluminum element and about 55% by the amount of charged silicon element.
Example 5:
the mother liquor recovered in example 4 was subjected to filtration recovery to remove the loss during recovery to give 130.0 g, which contained 1.67 g of NaOH, 8.12 g of KOH, 4.63 g of SiO in chemical analysis2115.00 g of water, the Al content being in accordance with NaAlO2The weight was calculated to be 0.06 g.
20 g of water, 0.33 g of sodium hydroxide and 1.88 g of potassium hydroxide were added thereto in this order, and dissolved by stirring. 0.65 g of sodium metaaluminate and 7.37 g of white carbon black are added. Stirring was continued at room temperature for 0.5 h. 0.60 g of seed crystal was added and stirred at room temperature to obtain a hydrogel.
The molar ratio of each raw material compound component in the hydrogel is calculated according to the corresponding oxide as follows:
M2O/SiO20.53, M represents the sum of Na and K, wherein NaOH/(NaOH + KOH) ═ 0.75.
SiO2/Al2O3＝40
H2O/SiO2＝37.5
The weight ratio of the seed crystal to the charged silica was 3%.
The hydrogel is transferred into a stainless steel kettle lined with a polytetrafluoroethylene lining for sealing, and hydrothermal crystallization is carried out for 2 days at 150 ℃. And after crystallization is finished, taking out the reaction kettle, naturally cooling, filtering and recovering the mother liquor. Washing the filter cake twice with a large amount of clear water, and drying to obtain the product.
The XRD powder diffraction pattern of the product is shown in figure 4, and the product is known to have the chabazite crystal structure.
Chemical analysis shows that the chemical composition of the product is | Na0.10K0.89|[Al1Si11.90O25.80]. The co-recovered product had a dry weight of 8.0 g, a yield of about 95% based on the amount of aluminum charged and about 56% based on the amount of silicon charged.
Example 6:
the mother liquor recovered in example 4 was removed by filtration and recovered130.0 g, containing 1.68 g NaOH, 8.08 g KOH, 4.50 g SiO in chemical analysis2And 115.00 g of water, wherein the content of Al is lower than the detection limit.
20 g of water, 0.32 g of sodium hydroxide and 1.92 g of potassium hydroxide are added in sequence, and stirred to dissolve. 0.82 g of sodium metaaluminate and 7.54 g of white carbon black are added. Stirring was continued at room temperature for 0.5 h. 0.60 g of seed crystal was added and stirred at room temperature to obtain a hydrogel.
The molar ratio of each raw material compound component in the hydrogel is calculated according to the corresponding oxide as follows:
M2O/SiO20.53, M represents the sum of Na and K, wherein NaOH/(NaOH + KOH) ═ 0.75.
SiO2/Al2O3＝40
H2O/SiO2＝37.5
The weight ratio of the seed crystal to the charged silica was 3%.
The hydrogel is transferred into a stainless steel kettle lined with a polytetrafluoroethylene lining for sealing, and hydrothermal crystallization is carried out for 2 days at the temperature of 110 ℃. And after crystallization is finished, taking out the reaction kettle, naturally cooling, filtering and recovering the mother liquor. Washing the filter cake twice with a large amount of clear water, and drying to obtain the product.
The XRD powder diffraction pattern of the product is shown in figure 4, and the product has chabazite crystal structure.
Chemical analysis shows that the chemical composition of the product is | Na0.28K0.70|[Al1Si11.60O25.20]. The co-recovered product had a dry weight of 7.5 g, and the yield was about 90% by the amount of charged aluminum element and about 52% by the amount of charged silicon element.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (8)
1. A method for synthesizing chabazite by a seed crystal guiding method and improving the utilization rate of raw materials comprises the following steps:
(1) preparing water, sodium hydroxide and potassium hydroxide into alkaline solution;
(2) dissolving an aluminum source compound in an alkaline solution at room temperature, slowly adding a silicon source compound at room temperature, and continuously stirring to obtain uniformly mixed hydrogel;
(3) adding a small amount of seed crystals into the hydrogel, and continuously stirring the mixture evenly at room temperature;
(4) sealing the mixture in a suitable container, and performing hydrothermal crystallization;
(5) separating and washing to obtain the aluminosilicate zeolite molecular sieve with chabazite structure;
(6) and (3) analyzing the concentration of sodium hydroxide, potassium hydroxide, silicon compounds (calculated by silicon dioxide) and aluminum compounds (calculated by aluminum oxide) in the mother liquor obtained by separation in the step (5), then returning to the step (1), sequentially adding a proper amount of water, sodium hydroxide, potassium hydroxide, aluminum compounds and silicon source compounds, then performing hydrothermal crystallization according to the steps (3) to (5) to obtain a chabazite product and recovering the product, wherein the mother liquor can be continuously recycled according to the method.
2. The method for synthesizing chabazite by the seed-guiding method and improving the utilization rate of raw materials according to claim 1, wherein the silicon source compound is: one or more of silica sol and white carbon black; the aluminum source compound is one or more of sodium metaaluminate and aluminum nitrate.
3. The method for preparing chabazite by seed-guided method and improving the utilization rate of raw materials according to claim 1, wherein the seed crystal is SSZ-13 molecular sieve.
4. The method for synthesizing chabazite by the seed-crystal-oriented method and improving the utilization rate of raw materials according to claim 1, wherein the amount of the SSZ-13 molecular sieve seed crystals added is 3% or less of the total amount of Si elements added.
5. The method for synthesizing chabazite by the seed-directing method and improving the utilization rate of raw materials according to claim 1, wherein the molar ratio of each component in the reaction mixture is as follows: m2O：SiO2＝0.50～0.55：1，SiO2：Al2O3＝20～40：1，H2O：SiO210-40: 1, wherein M is an alkali metal (Na, K).
6. The method for synthesizing chabazite by using the seed-directing method and improving the utilization rate of raw materials according to claim 5, wherein the ratio of NaOH/(NaOH + KOH) is 0.8-0, and the amount of KOH is not 0.
7. The method for synthesizing chabazite by using the seed-guiding method and improving the utilization rate of raw materials according to claim 1, wherein the crystallization temperature is 110-150 ℃ and the crystallization time is 1-2 days.
8. The method for synthesizing chabazite by the seed-directing method and improving the utilization rate of raw materials according to claim 1, wherein the silica-alumina ratio of the obtained molecular sieve product with the chabazite structure is far lower than that of the fed materials.
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| HIROYUKI IMAI ET AL.: "Direct crystallization of CHA-type zeolite from amorphous aluminosilicate gel by seed-assisted method in the absence of organic-structure-directing agents", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
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