CN114031092B - Preparation method of SAPO-20 molecular sieve - Google Patents
Preparation method of SAPO-20 molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 58
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 238000002425 crystallisation Methods 0.000 claims abstract description 30
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- -1 trimethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide Chemical compound 0.000 claims description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 235000011007 phosphoric acid Nutrition 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 abstract description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 15
- 238000004321 preservation Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 229910017119 AlPO Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a preparation method of an SAPO-20 molecular sieve, which comprises the following steps: (1) sol preparation: firstly, mixing and stirring an aluminum source, a phosphorus source and deionized water, and fully and uniformly mixing the aluminum source, the phosphorus source and the deionized water to obtain a mixed solution; sequentially and continuously adding a silicon source and a template agent R into the mixed solution, and continuously stirring to obtain sol; and (2) crystallization and post-treatment: transferring the sol to a crystallization kettle, and performing crystallization treatment under a hydrothermal condition; after crystallization, the SAPO-20 molecular sieve is obtained through suction filtration, washing, drying and roasting. The preparation method has simple steps and is easy to operate; the template R is novel organic ammonium, and compared with the conventional tetramethyl ammonium hydroxide template, the single-kettle yield of the preparation method of the SAPO-20 molecular sieve can be improved by 15-25%.
Description
Technical Field
The invention relates to a preparation method of an SAPO-20 molecular sieve, belonging to the technical field of molecular sieve preparation.
Background
In 1984, united states of America Carbonization (UCC) developed a series of silicoaluminophosphate molecular sieves (SAPO-n), which were made of SiO 2 、AlO 2 - 、PO 2 + Microporous crystals of three tetrahedral units, wherein n represents a different crystal structure. The molecular sieve comprises thirteen three-dimensional microporous framework structures, and the pore size of the molecular sieve is
The volume is 0.38-0.48 cm 3 (ii) in terms of/g. This is achieved byThe development of molecular sieve-like materials opens up new fields of molecular sieve materials, and can be used for catalysis, separation, ion exchange and the like. SAPO-20 molecular sieve is an important member of the molecular sieves, belongs to a cubic crystal system, has an SOD structure and has a pore volume of 0.40cm 3 The SAPO-20 molecular sieve is expected to be used in the fields of organic catalysis, gas separation, hydrogen storage and the like, wherein the/g is the molecular sieve with the pore size of about 0.3nm.
The synthesis of the SAPO-20 molecular sieve mainly adopts a hydrothermal crystallization method. The raw material for synthesizing the molecular sieve is mainly phosphoric acid as a phosphorus source; the silicon source mainly comprises silica sol, white carbon black, silicic acid, gaseous silicon dioxide and the like; the aluminum source mainly comprises pseudo-boehmite, aluminum isopropoxide, aluminum hydroxide, activated alumina and the like; the template is usually selected from tetramethylammonium hydroxide.
AlPO 4 The-20 molecular sieve has the same SOD structure as the SAPO-20 molecular sieve, except that no silicon atom is contained in the framework. Xu Wen et al found that only tetramethylammonium hydroxide could be directed to AlPO using tetramethylammonium hydroxide, tetraethylammonium hydroxide, cyclohexylamine, ethylenediamine, ethanol, etc. as templating agents under the same experimental conditions 4 -20 molecular sieve formation, thus tetramethylquaternary ammonium base (salt) is considered to form AlPO 4 -20 molecular sieves as the sole template, no tetramethylammonium hydroxide or tetramethylquaternary ammonium salt providing quaternary ammonium ion in the system, and no SOD structure in the aluminum phosphate system, (Xu Wen, dou Tao, wu Feng, alPO 4 -20 and the synthesis of their heteroatomic molecular sieves, proceedings of the university of taiyuan, 1989,3 (20): 21-26);
shotzian, et al, studied the influence of the type of template on the structural properties of SAPO-5 molecular sieves, and found that SAPO-5 molecular sieves and SAPO-34 molecular sieves with eight-membered rings can be synthesized by using triethylamine, tetraethylammonium hydroxide, tripropylamine, and dipropylamine as the template by adjusting the amount of the template, while SAPO-20 molecular sieves with six-membered rings can only be synthesized by using tetramethylammonium hydroxide as the template (Shotzian, wang Haitao, su Jixin, chen Fang, the type, concentration of the template, the influence of a silicon source on the structural properties of SAPO-5 molecular sieves, molecular catalysis, 1998, 12 (4): 246-252);
li Hongyuan et al also used tetramethylammonium hydroxideSAPO-20 molecular sieve is synthesized for the template agent, and the results show that the influence of the dosage of the template agent on the product is large when TMAOH/P 2 O 5 When the molar ratio is 1.25-3.75, the product is pure SAPO-20, and when TMAOH/P is adopted 2 O 5 When the ratio is less than 1, the product is dense phase AlPO 4 And TMAOH/P 2 O 5 When =5.0, the product is pure SAPO-42 (Li Hongyuan, liang Juan, liu Ziming, zhao Suqin, wang Ronghui, silicoaluminophosphate molecular sieves SAPO-11, synthesis of SAPO-34 and SAPO-20, catalyst bulletin, 1988,9 (1): 87-91);
U.S. Pat. No. 4,4440871 discloses a method for preparing SAPO-20 molecular sieve by hydrothermal synthesis. In the patent, tetramethyl ammonium hydroxide is also used as a template agent, orthophosphoric acid is used as a phosphorus source, silica sol or white carbon black is used as a silicon source, sodium metaaluminate or aluminum isopropoxide is used as an aluminum source, and the ratio of the amount of reactant substances is as follows: siO 2 2 ：Al 2 O 3 ：P 2 O 5 ：1.5TMAOH：50H 2 O, preparing an SAPO-20 molecular sieve product under the condition of crystallization for 68 hours at 125 ℃; orthophosphoric acid is used as a phosphorus source, silica sol is used as a silicon source, sodium metaaluminate is used as an aluminum source, and the ratio of the reactant substances is 4.0SiO 2 ：1.66Al 2 O 3 ：0.66P 2 O 5 ：2.2TMAOH：1.2Na 2 O:95H 2 And O, crystallizing at 200 ℃ for 68 hours to prepare the SAPO-20 molecular sieve product.
Therefore, the common template agent for synthesizing the SAPO-20 molecular sieve at home and abroad at present is tetramethyl ammonium hydroxide and is used in a high-water-content system (H) 2 O/Al 2 O 3 > 45) was synthesized. The invention mainly provides a novel organic ammonium template agent, and uses the template agent in a low water system (H) for the first time 2 O/Al 2 O 3 Between 30 and 50) to prepare a pure phase SAPO-20 molecular sieve.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the SAPO-20 molecular sieve, which can synthesize the SAPO-20 molecular sieve in a low-water-content system, and compared with the conventional method for preparing the SAPO-20 molecular sieve by using a tetramethyl ammonium hydroxide template agent, the single-kettle yield can be improved by 15-25%.
The technical scheme for solving the technical problems is as follows: a preparation method of SAPO-20 molecular sieve is characterized in that the preparation method of SAPO-20 molecular sieve comprises the following steps:
(1) Preparation of sol
Firstly, mixing and stirring an aluminum source, a phosphorus source and deionized water, and fully and uniformly mixing the aluminum source, the phosphorus source and the deionized water to obtain a mixed solution; then, sequentially and continuously adding a silicon source and a template agent R into the mixed solution, and continuously stirring to obtain sol;
(2) Crystallization and post-treatment
Transferring the sol to a crystallization kettle, and carrying out crystal bloom treatment under a hydrothermal condition; after crystallization is finished, carrying out suction filtration, washing, drying and roasting to obtain the SAPO-20 molecular sieve;
the template agent R is novel organic ammonium, and the novel organic ammonium is selected from one or more of trimethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide, trimethyl- (1,3,3,5,5-pentamethyl-piperidin-4-yl) ammonium hydroxide, triethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide, dimethyl-ethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide and diethyl-methyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide.
Preferably, the template agent R, the phosphorus source, the silicon source, the aluminum source and the deionized water are mixed according to the weight ratio of the template agent R: h 3 PO 4 ：SiO 2 ：Al 2 O 3 ：H 2 O =1.0-2.0:1.0-2.0:0.2-0.5:1:30-50 mol ratio.
Preferably, the template R is trimethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide.
Preferably, the aluminum source is one or more of pseudo-boehmite, aluminum hydroxide and aluminum isopropoxide.
Preferably, the phosphorus source is orthophosphoric acid.
Preferably, the silicon source is one or more of silica sol, ethyl orthosilicate and white carbon black.
Preferably, the specific operation steps of step (1) are as follows: firstly, mixing and stirring an aluminum source, a phosphorus source and deionized water for 0.5 to 1 hour at the temperature of between 10 and 35 ℃ to fully and uniformly mix the aluminum source, the phosphorus source and the deionized water to obtain a mixed solution; and then, sequentially and continuously adding a silicon source and a template agent R into the mixed solution, and continuously stirring for 0.5-1 h to obtain the sol.
Preferably, the specific operation steps of step (2) are as follows: transferring the sol into a crystallization kettle, crystallizing for 20-120 h under the condition of autogenous pressure hydrothermal at 160-220 ℃, and keeping the stirring speed of the crystallization kettle at 60-240 r/min; after crystallization, the SAPO-20 molecular sieve is obtained through suction filtration, washing, drying and roasting.
Preferably, the suction filtration and washing process is to add deionized water to wash the filter cake while suction filtration until the pH of the filtrate is 7; the drying process condition is drying for 4-8 hours at 90-120 ℃; the roasting process condition is that the temperature is programmed to 500-700 ℃ under the condition that the temperature rise rate is 3-5 ℃/min, and the temperature is kept for 3-5 h.
The invention has the beneficial effects that: the preparation method of the SAPO-20 molecular sieve has simple steps and is easy to operate; provides a new organic ammonium template agent for synthesizing the SAPO-20 molecular sieve, further enlarges the template agent range for preparing the SAPO-20 molecular sieve, and changes the condition that only tetramethyl ammonium hydroxide can be selected as the template agent at present; the template agent of the type can be used for synthesizing the SAPO-20 molecular sieve in a low water system, and compared with the tetramethyl ammonium hydroxide template agent, the single-kettle yield can be improved by 15-25%.
Drawings
FIG. 1 is the XRD pattern of SAPO-20 of example 3;
FIG. 2 is an SEM image of SAPO-20 of example 3.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Comparative example 1:
the method described in example 27 of the publication US 4440871A: 9.06g of pseudo-boehmite (Al) was added under stirring at room temperature 2 O 3 67.14%), 6.87g of phosphoric acid is added into 16.76g of deionized water, the stirring speed is increased to 600 revolutions per minute, and the stirring is carried out for 0.5h; 12.34g of silica Sol (SiO) 2 30 percent of TMAOH and 33.69g of tetramethylammonium hydroxide aqueous solution (25 percent of TMAOH) are added into the solution, the stirring speed is increased to 800 r/min, and uniform gel is formed after stirring for 1 hour; then the gel is transferred to a 100mL crystallization kettle, the stirring speed is set to be 120 r/min, and the temperature is raised to 125 ℃ for heat preservation and crystallization for 68h. And after crystallization is finished, carrying out post-treatment such as suction filtration, washing, drying, roasting and the like on the mixed solution to obtain a target product, and weighing the target product to obtain the product with the weight of about 29.6g.
Example 1:
trimethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide synthesis:
78.0g of 4-amino-2,2,6,6-tetramethylpiperidine, 156.0g of toluene and 125.0g of 30% aqueous formaldehyde were placed in a 500mL three-necked flask at room temperature. The internal temperature was raised to 60 ℃ and 82.5g of formic acid was slowly dropped into the system while stirring. After the addition, the system is slowly heated to 90 ℃, and is stirred for 120 hours under the condition of heat preservation. After the heat preservation is finished, the temperature is reduced to 25 ℃ in the system, and the layers are separated. The aqueous phase was extracted with 100g of toluene and the layers were separated and the toluene phase obtained and the organic phase from the reaction were combined. The combined organic phases were put into a 100ml three-necked flask, the temperature was raised to 40 ℃ and 53.15g of methyl bromide was added to the system. After the addition, the reaction is carried out for 2 hours at the temperature of 40-50 ℃. And after the heat preservation is finished, cooling to 25 ℃, and filtering to obtain a white solid. 30g of a white solid was taken, and 200g of water was added thereto and dissolved with stirring at room temperature. Passing through a resin exchange column of 30g to obtain the aqueous solution of the target product.
10.90g of pseudo-boehmite (Al) was added under stirring at room temperature 2 O 3 67.14%) into 11.41g deionized water, followed by 8.27g orthophosphoric acid (H) 3 PO 4 Content of 85%), increasing stirring speed to 600 rpm, stirring for 1 hr, and sequentially and continuously adding 7.17g of silica Sol (SiO) 2 30 percent of the content), 42.24g of trimethyl- (1,2,2,6,6-pentamethyl-piperidine-4-yl) ammonium hydroxide aqueous solution (the content of the template agent is 58.60 percent), the stirring speed is increased to 800 r/min, and uniform gel is formed after stirring for 1 h; then the gel is transferred to a 100mL crystallization kettle, the stirring speed is set to be 120 r/min, and the temperature is raised to 170 ℃ for crystallization by heat preservation for 24h. After crystallization is finished, the mixed solution is subjected to post-treatment such as suction filtration, washing, drying, roasting and the like to obtain a target product named A. XRD and SEM characterization tests show that the target product A prepared under the condition has a typical SOD type diffraction peak of SAPO-20 and high peak type sharp crystallinity, and as shown in figure 1, an SEM picture shows that the product appearance is a spherical crystal with the grain size of about 4 mu m. The one pot yield can be increased by about 21.7% compared to using tetramethylammonium hydroxide.
Example 2:
dimethyl-ethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide aqueous solution synthesis:
78.0g of 4-amino-2,2,6,6-tetramethylpiperidine, 156.0g of toluene and 125.0g of 30% aqueous formaldehyde were placed in a 500mL three-necked flask at room temperature. The internal temperature was raised to 60 ℃. Under stirring, 82.5g of formic acid was slowly dropped into the system. After the addition, the system is slowly heated to 90 ℃, and is stirred for 120 hours under the condition of heat preservation. After the heat preservation is finished, the temperature is reduced to 25 ℃ in the system, and the layers are separated. The aqueous phase was extracted with 100g of toluene and the layers were separated and the toluene phase obtained and the organic phase from the reaction were combined. The combined organic phases were put into a 100ml three-necked flask, the temperature was raised to 40 ℃ and 61.02g of bromoethane was added to the system. After the addition, the reaction is carried out for 2 hours at the temperature of 40-50 ℃. After the heat preservation is finished, the temperature is reduced to 25 ℃, and white solid is obtained by filtration. 30g of a white solid was taken, and 200g of water was added thereto and dissolved with stirring at room temperature. Passing through a resin exchange column of 30g to obtain the aqueous solution of the target product.
10.47g of pseudo-boehmite (Al) was added under stirring at room temperature 2 O 3 67.14%) was charged to 7.84g deionized water, followed by 7.94g orthophosphoric acid (H) 3 PO 4 Content of 85%), increasing stirring speed to 600 rpm, stirring for 1 hr, and sequentially and continuously adding 6.89g of silica Sol (SiO) 2 30 percent of the content), 46.86g of dimethyl-ethyl (1,2,2,6,6-pentamethyl-piperidine-4-yl) ammonium hydroxide aqueous solution (the content of the template agent is 57.50 percent), the stirring speed is increased to 800 r/min, and uniform gel is formed after stirring for 1 h; then the gel is transferred to a 100mL crystallization kettle, the stirring speed is set to be 120 r/min, and the temperature is raised to 160 ℃ for heat preservation and crystallization for 24h. After crystallization is finished, the mixed solution is subjected to post-treatment such as suction filtration, washing, drying, roasting and the like, and the SAPO-20 molecular sieve with the XRD spectrogram being a pure SOD structure is obtained. The one pot yield can be increased by about 16.7% compared to using tetramethylammonium hydroxide.
Example 3:
synthesis of aqueous triethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide:
78.0g of 4-amino-2,2,6,6-tetramethylpiperidine, 156.0g of toluene, 192.72.0g of 40% aqueous acetaldehyde solution were charged into a 500mL three-necked flask at room temperature. The internal temperature was raised to 60 ℃ and 105.0g of acetic acid was slowly dropped into the system while stirring. After the addition, the system is slowly heated to 90 ℃, and is stirred for 120 hours under the condition of heat preservation. After the heat preservation is finished, the temperature is reduced to 25 ℃ in the system, and the layers are separated. The aqueous phase was extracted with 100g of toluene and the layers were separated and the toluene phase obtained and the organic phase from the reaction were combined. The combined organic phases were put into a 100ml three-necked flask, the temperature was raised to 40 ℃ and 61.02g of bromoethane was added to the system. After the addition, the reaction is carried out for 2 hours at the temperature of 40-50 ℃. And after the heat preservation is finished, cooling to 25 ℃, and filtering to obtain a white solid. 30g of a white solid was taken, and 200g of water was added thereto and dissolved with stirring at room temperature. And passing through a resin exchange column of 30g to obtain the aqueous solution of the target product.
Under stirring at room temperature, 11.09g of pseudo-boehmite (Al) 2 O 3 67.14%) was charged into 12.49g of deionized water, followed by 8.41g of orthophosphoric acid (H) 3 PO 4 In a content of 85%), increasing the stirring speed to 600 revolutions/mlAfter stirring for 2 hours, 7.30g of silica Sol (SiO) was continuously added 2 30 percent of the total weight of the mixture), 40.71g of triethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide aqueous solution (the content of the template agent is 58.50 percent), the stirring speed is increased to 800 r/min, and uniform gel is formed after stirring for 1 hour; then the gel is transferred to a 100mL crystallization kettle, the stirring speed is set to be 120 r/min, and the temperature is raised to 180 ℃ for heat preservation and crystallization for 24h. After crystallization is finished, the mixed solution is subjected to post-treatment such as suction filtration, washing, drying, roasting and the like, and the SAPO-20 molecular sieve with the XRD spectrogram being a pure-phase SOD structure is obtained. The one pot yield can be increased by about 24.0% compared to using tetramethylammonium hydroxide.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A preparation method of SAPO-20 molecular sieve is characterized in that the preparation method of SAPO-20 molecular sieve comprises the following steps:
(1) Preparation of sol
Firstly, mixing and stirring an aluminum source, a phosphorus source and deionized water, and fully and uniformly mixing the aluminum source, the phosphorus source and the deionized water to obtain a mixed solution; sequentially and continuously adding a silicon source and a template agent R into the mixed solution, and continuously stirring to obtain sol;
wherein, the template agent R, the phosphorus source, the silicon source, the aluminum source and the deionized water are mixed according to the following ratio: h 3 PO 4 ：SiO 2 ：Al 2 O 3 ：H 2 O =1.0-2.0:1.0-2.0:0.2-0.5:1: adding in a molar ratio of 30-50;
(2) Crystallization and post-treatment
Transferring the sol to a crystallization kettle, and performing crystallization treatment under a hydrothermal condition; after crystallization, carrying out suction filtration, washing, drying and roasting to obtain the SAPO-20 molecular sieve;
the template agent R is organic ammonium, and the organic ammonium is selected from one or more of trimethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide, trimethyl- (1,3,3,5,5-pentamethyl-piperidin-4-yl) ammonium hydroxide, triethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide, dimethyl-ethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide and diethyl-methyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide.
2. The method for preparing SAPO-20 molecular sieve, according to claim 1, wherein the template R is trimethyl- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ammonium hydroxide.
3. The method for preparing the SAPO-20 molecular sieve of claim 1, wherein the aluminum source is one or more of pseudoboehmite, aluminum hydroxide and aluminum isopropoxide.
4. The method for preparing a SAPO-20 molecular sieve according to claim 1, wherein the phosphorus source is orthophosphoric acid.
5. The method for preparing SAPO-20 molecular sieve of claim 1, wherein the silicon source is one or more of silica sol, ethyl orthosilicate and silica white.
6. The method for preparing the SAPO-20 molecular sieve according to claim 1, wherein the specific operation steps of the step (1) are as follows: firstly, mixing and stirring an aluminum source, a phosphorus source and deionized water for 0.5 to 1 hour at the temperature of between 10 and 35 ℃ to fully and uniformly mix the aluminum source, the phosphorus source and the deionized water to obtain a mixed solution; and then, sequentially and continuously adding a silicon source and a template agent R into the mixed solution, and continuously stirring for 0.5-1 h to obtain the sol.
7. The method for preparing the SAPO-20 molecular sieve of claim 1, wherein the specific operation steps of the step (2) are as follows: transferring the sol into a crystallization kettle, crystallizing for 20-120 h under the self-generated pressure hydrothermal condition at 160-220 ℃, and keeping the stirring speed of the crystallization kettle at 60-240 r/min; after crystallization, the SAPO-20 molecular sieve is obtained through suction filtration, washing, drying and roasting.
8. The method for preparing the SAPO-20 molecular sieve of claim 7, wherein the suction filtration and washing process comprises adding deionized water to wash the filter cake while suction filtration until the pH of the filtrate is 7; the drying process condition is drying for 4-8 hours at 90-120 ℃; the roasting process condition is that the temperature is programmed to 500-700 ℃ under the condition that the temperature rise rate is 3-5 ℃/min, and the temperature is kept for 3-5 h.
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