CN109422271A - A method of synthesis has ATO structure aluminium phosphate molecular sieve - Google Patents
A method of synthesis has ATO structure aluminium phosphate molecular sieve Download PDFInfo
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- CN109422271A CN109422271A CN201710772122.6A CN201710772122A CN109422271A CN 109422271 A CN109422271 A CN 109422271A CN 201710772122 A CN201710772122 A CN 201710772122A CN 109422271 A CN109422271 A CN 109422271A
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- molecular sieve
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- ionic liquid
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- 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 79
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 58
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 26
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 18
- 229940001007 aluminium phosphate Drugs 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 38
- 230000008025 crystallization Effects 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002608 ionic liquid Substances 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- -1 imidazol ion Chemical class 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 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
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical class CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 241000219793 Trifolium Species 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- 241001101998 Galium Species 0.000 description 2
- 235000014820 Galium aparine Nutrition 0.000 description 2
- 241000612118 Samolus valerandi Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 210000003205 muscle Anatomy 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LRRVBLSOIBDURC-UHFFFAOYSA-M 1-butylpyridin-1-ium;acetate Chemical compound CC([O-])=O.CCCC[N+]1=CC=CC=C1 LRRVBLSOIBDURC-UHFFFAOYSA-M 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C01B37/04—Aluminophosphates [APO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of method that the present invention discloses molding ATO structure aluminium phosphate molecular sieve of the directly synthesis with intended shape, is related to technical field of molecular sieve preparation.Its main feature are as follows: silicon source, phosphorus source, Fluorine source, organic amine, ionic liquid and water are mixed in a certain ratio obtained gel, then by gained gel by intended shape processing molding, the formed body being made of completely molecular sieve can be obtained in formed gel crystallization under certain condition.Molding ATO structure aluminium phosphate molecular sieve is made in a step of the invention, simplifies preparation process.It is compared with the traditional method, this method preparation process is simple, and raw material availability is high, and waste liquid discharging amount is low, has broad application prospects.
Description
Technical field
The present invention relates to technical field of molecular sieve preparation, provide a kind of side of the synthesis with ATO structure aluminium phosphate molecular sieve
Method.
Background technique
Aluminium phosphate molecular sieve (the AlPO of ATO structure4- 31) there are non-crossing twelve-ring one-dimensional channels, pore size isBelong to trigonal system, space group R-3m, cell parameter is
Skeletal density isIts structure is by phosphorus oxygen tetrahedron PO4With aluminum-oxygen tetrahedron AlO4It constitutes.AlPO4- 31 points
Son sieve generally requires the finished granule that specific shape and size is made, finished product preparation process includes molecular sieve in industrial application
The synthesis of powder and the machine-shaping of particle.
AlPO4Hydrothermal synthesis method is used in the compound probability of -31 molecular sieve powders, this method takes water as a solvent, and material is pressed
Certain proportion is mixed to prepare colloidal sol, and colloidal sol between 80~200 DEG C and carries out crystallization under the self-generated pressure of water, and crystallization terminates
Afterwards, product is filtered, washed and is dried to obtain molecular sieve powder.Grain forming is needed molecular sieve powder and binder, plasticising
The additives such as agent, extrusion aid, pore creating material are mixed to get plastic body, then obtain by kneaded and formed, health, drying and roasting
Product.
Such as Yang Jie et al. is reported using aluminium isopropoxide as silicon source, phosphoric acid is phosphorus source, and di-n-butylamine is template, with
Al2O3:P2O5:DBA:H2Primogel is made in O=1:1:1.4:40 ratio, in hydro-thermal and under conditions of have Microwave-assisted firing,
The crystallization 2h at 130~180 DEG C after crystallization, is filtered, washed, is dried and is roasted, obtain AlPO4- 31 molecular sieves
(Chinese Journal of Catalysis,2011(32):1234-1241).Patent CN103285934A discloses one kind
Distillate hydrogenation deacidifying catalyst carrier containing molecular sieve and preparation method thereof, this method is by SAPO-31 molecular sieve and binder
It is mixed in a certain ratio, is formed by the method for granulation, then roast, obtain molded molecular sieve catalyst finished product, the catalyst
It can be used for distillate hydrogenation depickling reaction.
Above method first prepares molecular sieve powder, then is made and urges with additives mixed-forming, drying and roastings such as binders
Agent, adsorbent finished product, process flow is long, and process is complicated.In addition, molecular sieve water heat crystallization process carries out under high pressure, exist
Security risk；The filtration washing process of molecular sieve powder generates a large amount of waste water, causes environmental pollution；Due to the introducing of binder,
The content of molecular sieve is unable to reach 100% generally 60~80% in catalyst, adsorbent finished product, influences molecular sieve performance hair
It waves.
In order to solve problem above, people, which are directed to, simplifies molecular sieve catalyst, adsorbent preparation process and raising formed body
Numerous studies have been done in terms of the content two of middle molecular sieve.
Molecular sieve identical with raw material shape is directly made using having effigurate raw material in researchers, no longer needs into
Type can simplify molecular sieve catalyst, adsorbent preparation process.
Such as Sachse et al. is with SiO2Integral material is that raw material is prepared for molding ZSM-5 catalyst.This method is by SiO2It is whole
It is SiO that body material, which is placed in molar ratio,2:NaOH:NaAlO2:TPAOH:H2In the solution of O=1:0.15:0.09:0.004:33, in
Crystallization for 24 hours, obtains preformed catalyst (Micropor.Mesopor.Mater., 2011,140 (1-3): 58-68) at 150 DEG C.It should
Method uses SiO2Silicon source of the integral material as Zeolite synthesis, crystallization process keep solid phase, but silicon source NaAlO2Deng other raw materials
Still exist in aqueous solution, crystallization is still water-heat process.Although molecular sieve finished product maintains the shape of integral material, due to
Reaction raw materials are respectively in solid-liquid two-phase, and reaction process cannot be complete by mass transfer and limit, crystallization, and the content of ZSM-5 is only in finished product
38%.
FranziskaScheffler et al. is prepared for molding ZSM-5 catalyst by raw material of foamed aluminium integral material.It should
It is Na that foamed aluminium integral material is placed in molar ratio by method2O:TPABr:SiO2:H2The solution of O=0:423:0.055:1:72.4
In, crystallization for 24 hours, obtains preformed catalyst at 150 DEG C.The method uses foamed aluminium integral material for silicon source, other raw materials are also still
So in aqueous solution, the content of ZSM-5 also only has 13% (Micropor.Mesopor.Mater., 2004,67 (1): 53-9).
By part material, monolithic devices catalysis has been made in crystallization, a step to above method under hydrothermal conditions in the form of integral material
Agent, adsorbent, simplify preparation process.But other raw materials are still present in aqueous solution, crystallization is still water-heat process, is existed
Security risk；Reaction raw materials point are in solid-liquid two-phase, and reaction process is by mass transfer and limit, containing the raw material not changed in finished product,
Molecular sieve content is not high.In addition, these methods use integral material shape raw material, limited by raw material material, shape is single.And
The practical finished form of preformed catalyst, adsorbent is abundant at present, include spherical shape, bar shaped, cylinder, honeycombed, bunge bedstraw herb shape,
Cloverleaf pattern, external tooth wheel shape, non-porous external tooth wheel shape, it is quincunx, porous it is quincunx, seven apertures in the human head is spherical, non-porous spherical, seven muscle wheels
Shape, four hole shapes, four leaf butterfly shapes etc..
In order to improve molecular sieve catalyst, in adsorbent finished product molecular sieve content, researchers do a lot of work, will
The additives crystallization such as the binder of forming process addition are molecular sieve.
Such as X-type molecular sieve powder is mixed and is granulated with metakaolin by Kristin Schumann et al., is then passed through
At X-type molecular sieve particle, adsorbent finished product can be obtained using roasting in the convert by the method for hydrothermal synthesis
(Micropor.Mesopor.Mater.,2012,154,119-123)。
Patent CN102372281A discloses a kind of preparation method of ZSM-5/ β composite molecular sieve catalyst.This method is by β
After molecular sieve and binder mixed-forming, further in the aqueous solution containing organic amine, hydrothermal treatment is converted into integrated
ZSM-5/ β composite molecular sieve catalyst, obtains finished catalyst using roasting.
Above method formed body obtained crystallization again after mixing molecular sieve powder with binder, is transformed into binder
Molecular sieve.Though the available formed body being made of completely molecular sieve of the method, there is still a need for synthesis of molecular sieve original powders；Forming process
Crystallization steps are increased, manufacturing cost is improved.
The present invention proposes a kind of preforming synthetic method of complete molecular sieve, can reach simplified molecular sieve catalyst, suction simultaneously
Attached dose of preparation process and the target for improving molecular sieve content in formed body.Present invention is particularly directed to the aluminophosphate moleculars of ATO structure
Sieve, provides a kind of preforming synthetic method.
Summary of the invention
Present invention aims at the process flow for simplifying molecular sieve catalyst, adsorbent preparation, directly preparation has expectation
The pure molecular screen material of shape provides a kind of preforming synthetic method of aluminium phosphate molecular sieve with ATO structure.
The scheme that the present invention solves above-mentioned technical problem is as follows:
A method of the ATO structure aluminium phosphate molecular sieve with International Zeolite Association's confirmation is synthesized, synthesized gel rubber is pressed
The molding of intended shape working process, then crystallization obtain molded molecular sieve consistent with formed gel shape, include the following steps,
(1) silicon source, phosphorus source, Fluorine source, organic amine, ionic liquid and water are pressed into Al2O3:P2O5:F-: organic amine: ionic liquid:
H2O=1:0.2~7:0.01~10:0.01~8:0.005~6:2~90 molar ratio is mixed to prepare gel,
(2) gel made from step (1) is processed into the formed gel with required shape,
(3) formed gel made from step (2) is placed in closed container, at 100~260 DEG C crystallization 10min~
10d obtains the molded molecular sieve with ATO topological structure.
According to the method described in claim 1, it is characterized by: silicon source, phosphorus source, Fluorine source, organic amine, organic amine, ion
The molar ratio of liquid and water is Al2O3:P2O5:F-: organic amine: ionic liquid: H2O=1:0.4~3.0:0.02~2.5:0.1~
7.0:0.02~3.0:25~60.
Organic amine of the present invention is di-n-propylamine, di-n-butylamine, two n-amylamines, one or both of two n-hexylamines
More than.
The preparation of gel of the present invention uses this field routine operation method, for example in certain temperature and strong stirring bar
Under part, silicon source, phosphorus source, Fluorine source, organic amine, ionic liquid are added in deionized water mix according to a certain percentage, is mixed
Aqueous gel uniformly containing silicon source, phosphorus source, Fluorine source, organic amine and ionic liquid.
Gel forming of the present invention be this field routine operation, be for example extruded moulding, compression forming, oil column at
Type, rotational forming, spray shaping or granulating, the shape of obtained formed gel can be spherical shape, bar shaped, cylinder, honeycombed,
Bunge bedstraw herb shape, cloverleaf pattern, external tooth wheel shape, non-porous external tooth wheel shape, it is quincunx, porous it is quincunx, seven apertures in the human head is spherical, non-porous spherical,
Seven muscle wheel shapes, four hole shapes or four leaf butterfly shapes etc..The shape and size specifically used are selected according to actual service conditions requirement
It determines.Gel of the present invention can carry out the pretreatment of certain forms before forming operation, improve its plasticity, with guarantee at
The convenient operation of type process.Gel can be for example aged to 3~6h at normal temperature, then handled under the conditions of 50 DEG C~110 DEG C
5h~12h removes water a part of in gel, obtains the solid of shaping, then processing and forming.
It needs to add ionic liquid in gel synthesized by the present invention, one or more kinds of ionic liquids can be added
Body.The anion of added ionic liquid can be Br-、I-、Cl-、CH3COO-One or both of
More than；Cation is alkyl-substituted imidazol ion [Rim]+, alkyl-substituted pyridinium ion [Rpy]+, quaternary ammonium alkyl salt ion
[NR4]+One or more of, R is the alkyl containing 1 to 16 carbon.
Silicon source of the present invention be boehmite, activated alumina, aluminium hydroxide, in aluminium isopropoxide, aluminum sulfate or
The one or more of aluminum nitrate.
Phosphorus source of the present invention be one or both of phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, triammonium phosphate with
On.
Fluorine source of the present invention is one or more of hydrofluoric acid, sodium fluoride, ammonium fluoride.
The preferred crystallization temperature of crystallization process of the present invention is 110~230 DEG C, and preferably crystallization time is 30min~7d.It is brilliant
Formed gel is placed in the pressure resistant vessel of this field routine and carries out by change process, and a certain amount of water can be pre-placed in container,
But it is not necessary to water is directly contacted with formed gel.Crystallization process uses the heating method of this field routine, for example, oil bath
Heating, baking oven heating and microwave heating.
Crystallization terminates, and mold compound obtained by the present invention is not necessarily to filtration washing.Crystallization product maintains formed gel phase
Same shape and size, are made of molecular sieve completely, and sample molecule sieve skeleton structure is International Zeolite Association in following embodiments
The AFO structure of confirmation.Crystallization product does powder x-ray diffraction after crushing, diffraction maximum position and relatively strong and weak as follows:
To help to understand the present invention, " preforming " term is defined below.The term of this definition has the present invention related
The normally understood meaning of the those of ordinary skill in field.
Unless otherwise stated, " preforming " refers in advance by gel used in synthesis of molecular sieve, by compressing, squeezing herein
The methods of out, rotate, is spraying, it is processed into the process or step of the formed gel with certain shapes, size and mechanical strength.
In conclusion the present invention provides the preformation method that a kind of synthesis has the aluminium phosphate molecular sieve of ATO structure, tool
It has the following advantages:
One step is made molded molecular sieve and simplifies catalyst or adsorbent preparation process.Formed body is completely by molecular sieve structure
At improving the content of molecular sieve in formed body, avoid the filtration washing step of conventional molecular sieve production process, discharging of waste liquid
Measure it is low, it is environmental-friendly.
Detailed description of the invention
Fig. 1 is that the in kind of cylinder bar shaped ATO type aluminium phosphate molecular sieve prepared by the pre-shaping method of the embodiment of the present invention 1 shines
Piece.
Fig. 2 is that the in kind of clover bar shaped ATO type aluminium phosphate molecular sieve prepared by the pre-shaping method of the embodiment of the present invention 2 shines
Piece.
Specific embodiment
The present invention is described in detail below by example, but the method for the present invention is without being limited thereto, the present invention cannot be protected
Range be construed as limiting.
1 embodiment of the present invention 1~5 of table and synthesis condition.
Embodiment 1
By 17.35g boehmite (78.6wt%Al2O3) be placed in 250ml beaker, 95.39g deionized water, room is added
It is stirred 30 minutes under the conditions of temperature；The phosphoric acid that 33.90g concentration is 85wt% is added, stirs 3 hours；Adding 1.34g concentration is
The hydrofluoric acid of 40wt% continues stirring 30 minutes；17.47g di-n-butylamine is added, is stirred 30 minutes；It is eventually adding 28.09g
1- ethyl -3- methy limidazolium ionic liquid.Said mixture is stirred evenly into gelled, is then dried under the conditions of 90 DEG C
It is 30 minutes roasting.The plasticity gel mixture that aforesaid operations are obtained uses double screw banded extruder, is extruded into the cylindrical bars of diameter 2mm
Shape.Obtained forming cylinder bar shaped gel is placed in the crystallizing kettle with polytetrafluoroethylkettle kettle lining, the closed crystalline substance at 200 DEG C
Change 3 days.
Crystallizing kettle is cooled to room temperature after crystallization, obtains the cylindrical bars shape molded molecular sieve of diameter about 2mm.It will molding
Molecular sieve grind into powder does XRD analysis, which is ATO type aluminium phosphate molecular sieve.Molded molecular sieve is cylinder bar shaped, such as
Shown in Fig. 1.
Embodiment 2
By 17.35g boehmite (78.6wt%Al2O3) be placed in 250ml beaker, 129.23g deionized water is added,
It stirs 30 minutes under room temperature；The phosphoric acid that 79.62g concentration is 85wt% and the biphosphate that 9.23g purity is 99% is added
Ammonium stirs 3 hours；The hydrofluoric acid that 0.14g concentration is 40wt% is added, stirring 30 minutes is continued；Add 47.33g bis- just
Propylamine and 60.46g di-n-butylamine stir 30 minutes；It is eventually adding 0.62g N- butyl-pyridinium acetate ionic liquid.It will be above-mentioned
Mixture stirs evenly gelled, then toasts 30 minutes under the conditions of 100 DEG C.The plasticity gel that aforesaid operations are obtained
Mixture uses double screw banded extruder, is extruded into clover bar shaped.Obtained molding clover bar shaped gel is placed in poly-
In the crystallizing kettle of tetrafluoroethene kettle lining, closed crystallization 7 days at 230 DEG C.
Crystallizing kettle is cooled to room temperature after crystallization, obtains clover bar shaped molded molecular sieve.Molded molecular sieve is ground
It clays into power and does XRD analysis, which is ATO type aluminium phosphate molecular sieve.Molded molecular sieve is clover bar shaped, such as Fig. 2 institute
Show.
Embodiment 3
By 17.35g boehmite (78.6wt%Al2O3) be placed in 250ml beaker, 44.23g deionized water, room is added
It is stirred 30 minutes under the conditions of temperature；The phosphoric acid that 12.33g concentration is 85wt% is added, stirs 3 hours；Adding 15.04g concentration is
The ammonium fluoride that the hydrofluoric acid and 1.25g purity of 40wt% is 99% continues stirring 30 minutes；Bis- n-amylamine of 2.10g is added, is stirred
It mixes 30 minutes；It is eventually adding 45.31g 1- butyl -3- methyl imidazolium tetrafluoroborate ionic liquid and 38.31g 1- ethyl -3-
Methy limidazolium ionic liquid.Said mixture is stirred evenly into gelled, is then toasted 30 minutes under the conditions of 75 DEG C.
The plasticity gel mixture roller forming that aforesaid operations are obtained,.Obtained molding spherical gel is placed in poly- four
In the crystallizing kettle of vinyl fluoride kettle lining, closed crystallization 30 minutes at 230 DEG C.
Crystallizing kettle is cooled to room temperature after crystallization, obtains spherical molded molecular sieve.Molded molecular sieve is pulverized
XRD analysis is done at end, which is ATO type aluminium phosphate molecular sieve.
Embodiment 4
By 17.35g boehmite (78.6wt%Al2O3) be placed in 250ml beaker, 32.03g deionized water, room is added
It is stirred 30 minutes under the conditions of temperature；The phosphoric acid that 12.33g concentration is 85wt% is added, stirs 3 hours；Adding 16.71g concentration is
The hydrofluoric acid of 40wt% continues stirring 30 minutes；Bis- n-hexylamine of 80.71g again stirs 30 minutes；It is eventually adding 0.44g tetraethyl
Ammonium chloride ionic liquid.Said mixture is stirred evenly into gelled, is then toasted 30 minutes under the conditions of 75 DEG C.It will be above-mentioned
Obtained plasticity gel mixture is operated using single-screw extruder, is extruded into honeycombed.Obtained formed honeycomb shape is coagulated
Glue is placed in the crystallizing kettle with polytetrafluoroethylkettle kettle lining, closed crystallization 30 minutes at 230 DEG C.
Crystallizing kettle is cooled to room temperature after crystallization, obtains honeycombed molded molecular sieve.Molded molecular sieve is ground into
Powder does XRD analysis, which is ATO type aluminium phosphate molecular sieve.
Embodiment 5
By 14.74g boehmite (78.6wt%Al2O3) and 4.09g purity be 99% aluminium isopropoxide be placed in 250ml
In beaker, 103.37g deionized water is added, stirs 30 minutes under room temperature；The phosphoric acid that 12.33g concentration is 85wt% is added,
Stirring 3 hours；The hydrofluoric acid that 0.14g concentration is 40wt% is added, stirring 30 minutes is continued；1.73g di-n-butylamine is added,
Stirring 30 minutes；It is eventually adding 0.28g nitric acid second ammonium ion liquid.Said mixture is stirred evenly into gelled, then in
It is toasted 30 minutes under the conditions of 80 DEG C.The plasticity gel mixture that aforesaid operations obtain is prepared into spherical shape using oil-drop method
Particle.Obtained shaped granule shape gel is placed in the crystallizing kettle with polytetrafluoroethylkettle kettle lining, the closed crystalline substance at 110 DEG C
Change 7 days.
Crystallizing kettle is cooled to room temperature after crystallization, obtains graininess molded molecular sieve.Molded molecular sieve is ground into
Powder does XRD analysis, which is ATO type aluminium phosphate molecular sieve.
The XRD diffraction maximum position of sample and relatively strong and weak in 2 embodiment of the present invention 1~5 of table.
As seen from the above table, the ATO type aluminum phosphate of pure phase can be prepared in the Reaction conditions range that this method is stated
Molecular sieve.
Claims (9)
1. a kind of method that synthesis has ATO structure aluminium phosphate molecular sieve, it is characterised in that: add synthesized gel rubber by intended shape
Work processing molding, then crystallization obtain molded molecular sieve consistent with formed gel shape, include the following steps,
(1) silicon source, phosphorus source, Fluorine source, organic amine, ionic liquid and water are pressed into Al2O3:P2O5:F-: organic amine: ionic liquid: H2O
=1:0.2~7:0.01~10:0.01~8:0.005~6:2~90 molar ratio is mixed to prepare gel,
(2) gel made from step (1) is processed into the formed gel with required shape,
(3) formed gel made from step (2) is placed in closed container, crystallization 10min~10d, obtains at 100~260 DEG C
To the molded molecular sieve of the ATO topological structure confirmed with International Zeolite Association.
2. according to the method described in claim 1, it is characterized by: silicon source, phosphorus source, Fluorine source, organic amine, ionic liquid and water
Molar ratio is Al2O3:P2O5:F-: organic amine: ionic liquid: H2O=1:0.4~3.0:0.02~2.5:0.1~7.0:0.02~
3.0:25~60.
3. according to the method described in claim 1, it is characterized by: organic amine be di-n-propylamine, di-n-butylamine, two n-amylamines,
One or more of two n-hexylamines.
4. directly brilliant according to the method described in claim 1, it is characterized by: synthesized gel rubber is pre-processed into intended shape
Change a step and the formed body being made of molecular sieve is made.
5. added according to the method described in claim 1, it is characterized by: need to add ionic liquid in synthesized gel rubber
The anion of ionic liquid is Br-、I-、Cl-、CH3COO-One or more of, cation is alkyl
Substituted imidazol ion [Rim]+, alkyl-substituted pyridinium ion [Rpy]+, quaternary ammonium alkyl salt ion [NR4]+One of or two
Kind or more, R is the alkyl of C1-C16.
6. according to claim 1 with the method, it is characterised in that: silicon source be boehmite, activated alumina, hydroxide
In aluminium, aluminium isopropoxide, the one or more of aluminum sulfate or aluminum nitrate.
7. according to claim 1 with the method, it is characterised in that: phosphorus source be phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate,
One or more of triammonium phosphate.
8. according to the method described in claim 1, it is characterized by: Fluorine source be one of hydrofluoric acid, ammonium fluoride, sodium fluoride or
It is two or more.
9. according to the method described in claim 1, it is characterized by: the crystallization temperature of the crystallization process be 110~230 DEG C,
Crystallization time is 30min~7d.
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| CN104163436A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Method for synthesizing monolithic 4A molecular sieve by dry glue process |
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| CN104163436A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Method for synthesizing monolithic 4A molecular sieve by dry glue process |
Non-Patent Citations (3)
| Title |
|---|
| 杨杰: "ATO分子筛的微波合成及正癸烷加氢异构化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 沈玉龙，蔡明建: "《绿色化学（第三版）》", 28 April 2016, 中国环境出版社 * |
| 高滋主编: "《沸石催化与分离技术》", 30 November 1999, 中国石化出版社 * |
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