CN110182823A - A method of reducing aluminium phosphate molecular sieve size of microcrystal - Google Patents
A method of reducing aluminium phosphate molecular sieve size of microcrystal Download PDFInfo
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- CN110182823A CN110182823A CN201910427923.8A CN201910427923A CN110182823A CN 110182823 A CN110182823 A CN 110182823A CN 201910427923 A CN201910427923 A CN 201910427923A CN 110182823 A CN110182823 A CN 110182823A
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- molecular sieve
- sapo
- crystallization
- crystal seed
- aluminium
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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 87
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 29
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title abstract description 14
- 229940001007 aluminium phosphate Drugs 0.000 title abstract description 14
- 239000013081 microcrystal Substances 0.000 title description 3
- 238000002425 crystallisation Methods 0.000 claims abstract description 67
- 230000008025 crystallization Effects 0.000 claims abstract description 64
- 239000013078 crystal Substances 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012452 mother liquor Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000004411 aluminium Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 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
- 230000000694 effects Effects 0.000 claims description 4
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008279 sol Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- 229910001648 diaspore Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 13
- 239000000047 product Substances 0.000 description 21
- 239000012265 solid product Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 12
- 241000269350 Anura Species 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 235000019580 granularity Nutrition 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical class ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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]
-
- 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
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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]
-
- 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
-
- 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
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of methods that can reduce aluminium phosphate molecular sieve crystal particle diameter.This method carries out secondary hydrothermal crystallizing preparation by the way that crystal seed is added into crystallization liquid.Specifically by silicon source, silicon source, phosphorus source, the phosphate aluminium molecular sieve that can be used as crystal seed, metal salt solution, water or preparing the crystallization mother liquor after crystal seed and being uniformly mixed, Primogel crystallization liquid then is mixed to prepare with organic amine template R；Crystallization liquid is fitted into crystallization in hydrothermal synthesis kettle, the isolated small particle molecular sieve.This method is simple, efficiently, can prepare at least that crystal particle diameter reduces 50% or more small particle molecular sieve in one dimension under without using expensive tetraethyl ammonium hydroxide organic amine template, while having universality.
Description
Technical field
The present invention relates to the preparation method fields of molecular screen material, and in particular to a kind of reduction aluminium phosphate molecular sieve crystal grain grain
The preparation method of diameter.
Background technique
Nineteen eighty-two, U.S. combinating carbide company (UCC) successfully develop serial aluminium phosphate molecular sieve, are known as the third generation
Molecular sieve.This kind of well-regulated cellular structure of molecular sieve and good thermal stability and hydrothermal stability, meanwhile, pass through by
Hetero atom is introduced into the skeleton of molecular sieve, is replaced Al or P atom, the acid modulation of molecular sieve be may be implemented, to widen it
Application durings petrochemical industry, coal chemical industry etc..This molecular sieve analog has been widely used as catalyst, adsorbent and catalysis at present
Agent carrier, the great attention by domestic and international material science research field and industry.Such as: SAPO-34, SAPO-18 molecular sieve
Applied in oxygenatedchemicals olefine reaction；SAPO-37 molecular sieve shows higher activity to petroleum cracking；SAPO-11
Molecular sieve is shown solely in the petrochemical industries such as the skeletal isomerization of low-carbon alkanes and alkene, catalytic cracking and isomerization dewaxing
Special catalytic performance, application of especially succeeding in the isomerization dewaxing technique of lube cut；What metal ion replaced
MeAPO4-5 and MeAPO4-11 molecular sieve has the oxidation-reduction quality of metal ion, and it is anti-that MeAPO4-5 can be applied to hydrocarbon oxidation
It answers, MeAPO4-11 Pyrogentisinic Acid's hydroxylating has preferable catalytic performance.
But the size of microcrystal of gained aluminium phosphate molecular sieve is prepared generally several micro- using common hydrothermal synthesis method
Rice in addition more than ten microns, specific surface area is relatively small, and is unfavorable for the diffusion of reactants and products, to influence catalyst
Catalytic performance and product distribution.It is many studies have shown that external surface area not only can be improved in the molecular sieve carrier of little crystal grain, increase
Outer surface orifice number to improve the specific activity of molecular sieve, and is conducive to shorten the diffusion path of reactant and product molecule,
The limitation for weakening diffusion, extends the service life of catalyst, improves the anti-carbon deposit deactivation of catalyst.Therefore, exploitation is simple, high
Effect, lower-cost synthetic method prepare small crystal grain molecular sieve and have great importance.
Patent CN101823728 provides a kind of preparation method of fine grain SAPO-34 molecular sieve.This method passes through hydro-thermal
Synthesized gel rubber and aging process recycle hydrogen peroxide oxidation processing, and it is 300~500nm that partial size finally, which is made, by ultrasonic disperse
SAPO-34 molecular sieve.The organic amine template that this method uses is tetraethyl ammonium hydroxide.This method process is complicated, uses
A variety of processing modes, and because use the cost that expensive template considerably increases molecular sieve.Simultaneously use TEAOH as
Template, product yield is lower, and size distribution is wide.
Patent WO2003/048042 reports mixed using ethyl orthosilicate as silicon source, TEAOH or TEAOH and DPA
The method that object is closed as template obtains small grain size SAPO-34 molecular sieve, but SEM photograph is not provided in text to prove.
Patent CN104340985 provides a kind of by the way that crystal seed is added using secondary crystallization method preparation little crystal grain SAPO molecule
The method of sieve, crystal seed used in this method are by the SAPO molecular sieve analog of pretreatment (preferred Mechanical Crushing), granularity is 10~
The particle of 800nm.This method has compared with strict requirements the granularity of crystal seed, it is therefore desirable to pre-treatment step.
Patent CN104229829 promotes the synthesis of small crystal grain molecular sieve by the way that the crystal seed of defect sturcture is added, while
Multistep crystallization is all made of in the synthesis of crystal seed and the synthesis of small crystal grain molecular sieve.This method there are certain requirements the crystal seed, be
SAPO-34 molecular sieve with defect sturcture, and the synthesis of crystal seed and the synthesis step slightly complicated of product.
Catalytic effect of the SAPO-18 molecular sieve in methanol to olefins reaction is also very significant.Patent CN105271302 is used
Composite mould plate agent, by n,N-diisopropylethylamine and selected from least one of triethylamine, diethylamine and isopropylamine template group
It closes and uses, by ageing and crystallization steps, synthesize little crystal grain SAPO-18 molecular sieve.The molecular sieve is in methanol to olefins reaction
In show excellent catalytic performance and longer service life.But this method define composite mould plate agent first is that N, N- diisopropyl
Ethamine, this will greatly increase cost of material.
In the preparation of little crystal grain aluminium phosphate molecular sieve described above, exist or cost of material is high or synthesis process is complicated,
The problems such as yield is low, this is all unfavorable for the production application of product, therefore seeks one kind and be simple and efficient, be at low cost, and energy
The aluminium phosphate molecular sieve novel preparation method for enough promoting catalytic performance, has great importance.The method of the present invention is used by crystalline substance
Change in liquid and crystal seed is added, carries out secondary hydrothermal crystallizing preparation small particle molecular sieve.In addition to partial size reduces by 50% or more, it is also possible to adjust
Become the composition of molecular sieve, to improve the catalytic life and performance of the catalyst of its preparation；Template can not use tetraethyl
Ammonium hydroxide, while a crystallization mother liquor is used, raw material availability is improved, plays the role of reducing cost.
Summary of the invention
For this purpose, inventor after study and explore, have found the synthesizing small-grain phosphoric acid that a kind of process is simple, universality is strong
The new method of aluminum molecular screen, not only catalytic performance is improved the molecular sieve prepared using this method, and single pass life also obviously prolongs
It is long.
The purpose of the present invention is by the following technical programs to solve.
Little crystal grain aluminium phosphate molecular sieve of the present invention, synthesis step are as follows.
A) by silicon source, silicon source, phosphorus source, the phosphate aluminium molecular sieve that can be used as crystal seed, metal salt solution, water or after preparing crystal seed
Crystallization mother liquor is uniformly mixed, and is then mixed to prepare Primogel crystallization liquid I with organic amine template R；Each component in crystallization liquid I
Mol ratio is as follows: SiO2 : Al2O3 : P2O5 : R : H2O: Me=(0~2): (0~2): (0~2): (0.1
~20): (0~100): (0~1.5), and when water is 0, it must be used in raw material and prepare the crystallization mother liquor after crystal seed；
B) aging 0~for 24 hours at room temperature~140 DEG C, the crystallization liquid II after obtaining aging by initial crystallization liquid I；
C) by the crystallization liquid II after aging, 2~40h of hydrothermal crystallizing, crystallization temperature are at least high compared with aging temperature at 140~220 DEG C
20℃；
D) after crystallization, small crystal grain molecular sieve is obtained through cooling, washing, drying, roasting.
Can be used as in technical solution of the present invention, described in step a) crystal seed (silicon) phosphate aluminium molecular sieve be selected from SAPO-5,
In SAPO-11, SAPO-18, SAPO-34, SAPO-35, SAPO-44, MeAPSO and AlPO4-5, AlPO4-11 and MeAPO4
It is one or more of.
In technical solution of the present invention, silicon source described in step a) be selected from silica solution, ethyl orthosilicate, active silica,
The mixing of one or more of kaolin through overactivation or the gangue through overactivation；Source of aluminium be selected from boehmite,
The mixing of one or more of boehmite, Aluminum sol, aluminium oxide, aluminium hydroxide, aluminum soluble salt or aluminium isopropoxide；Institute
State the mixing that phosphorus source is selected from one or more of phosphoric acid, phosphorous acid, phosphorus pentoxide；The template is selected from diethylamine, three
Ethamine, morpholine, tetraethyl ammonium hydroxide, hexamethylene imine, N, N- diisopropylethylamine, cyclohexylamine, diisopropylamine, two positive third
The mixing of one or more of amine or Tri-n-Propylamine, and the organic amine template R is not preferably tetraethyl ammonium hydroxide；Institute
The mixing that metal salt is selected from one or more of the nitrate of metal, sulfate, acetate, chloro salt is stated, the metal salt is easy
It is dissolved in water.
It can be used as (silicon) phosphate aluminium molecular sieve and Primogel crystallization of crystal seed in technical solution of the present invention, described in step a)
The mass ratio of liquid is 0.03~0.3: 1.
Using molecular sieve made from the above method compared with molecular sieve made from conventional hydrothermal synthetic method, at least in one dimension
Crystal particle diameter reduce 50% or more, wherein the small particle molecular sieve be selected from SAPO-5, SAPO-11, SAPO-18, SAPO-34,
One or more of SAPO-35, SAPO-44, MeAPSO and AlPO4-5, AlPO4-11 and MeAPO4.
The present invention provides a kind of to prepare little crystal grain aluminium phosphate molecular sieve by secondary crystallization simply, with universality
Method, this method prepare the secondary crystallization liquid for having crystal seed by a certain percentage first, then carry out crystallization.
Compared with prior art, the invention has the advantages that.
1. the present invention can be without using expensive tetraethyl ammonium hydroxide template or other solvents, auxiliary agent, surfactant
It can also be prepared by a crystallization mother liquor for preparing crystal seed Deng, crystallization liquid, not only save the cost but also environmentally friendly, while improve the comprehensive of raw material
Close utilization rate.
2. the present invention is very low to requirements such as the type of crystal seed and granularities, synthetic method is simple and practical, universality is strong.
3. the composition that the present invention can effectively adjust molecular sieve by secondary crystallization.
4. the present invention can greatly shorten crystallization time by crystal seed secondary crystallization method.
5. the molecular sieve prepared by the method for the present invention, can effectively reduce the molecular sieve prepared by former synthetic method and
The partial size of seed molecule sieve, improves the value of product.
Detailed description of the invention
Fig. 1 and Fig. 2 is SAPO-34 points in synthesis according to a conventional method and embodiment 3 prepared according to the methods of the invention respectively
The SEM photograph of son sieve sample.
Fig. 3 and Fig. 4 is SAPO-18 points in synthesis according to a conventional method and embodiment 9 prepared according to the methods of the invention respectively
The SEM photograph of son sieve sample.
Fig. 5 and Fig. 6 is FeAPO4-5 in synthesis according to a conventional method and embodiment 15 prepared according to the methods of the invention respectively
The SEM photograph of sieve sample.
Fig. 7 is the XRD spectra of above-mentioned SAPO-34, SAPO-18 and FeAPO4-5 molecular sieve.
Specific embodiment
Secondary crystallization method is used provided by the present invention for the method for reducing aluminium phosphate molecular sieve partial size.Specifically will
Silicon source, silicon source, phosphorus source, the phosphate aluminium molecular sieve that can be used as crystal seed, metal salt solution, water prepare the crystallization mother liquor mixing after crystal seed
Uniformly, crystallization liquid then is mixed to prepare with organic amine template R；Crystallization liquid is fitted into hydrothermal synthesis kettle brilliant under certain condition
Change, isolated small particle molecular sieve.Wherein, it can be as the phosphate aluminium molecular sieve of crystal seed commercially available, be also possible to independently synthesize
Molecular sieve.And the molecular sieve can be the dry molecular sieves of wet cake or non-removed template method or dividing for template is fallen in roasting removing
Son sieve.Meanwhile the crystallization liquid after a crystallization is after separation, solid product and crystallization mother liquor can be used as raw material and carry out two para-crystals
Change, on the one hand product property can be adjusted by the change of secondary crystallization raw material proportioning and condition, original on the other hand can be improved
Expect utilization rate, increases product yield.Third, under the premise of not increasing other any processing steps, the catalysis for promoting product is living
Property.
The following examples will be further described the present invention, but not thereby limit the invention.
Embodiment 1: as the source aluminium phosphate molecular sieve sample (a)~(l) of crystal seed or preparation.
Sample (a) is the sheet SAPO-34 molecular sieve that in patent CN106477595A prepared by embodiment 6, crystal size ruler
Very little is 1.5 μm or so, with a thickness of 50~200nm.
Sample (b) is available from the SAPO-11 molecular sieve of Shanghai Shen Tan environmental friendly material Co., Ltd, and 1-5 μm of crystal particle diameter.
Sample (c)
12.3g boehmite is added into beaker, 18.5g phosphoric acid, 7.4g silica solution, 26.8g triethylamine and 75g water are mixed
Merging stirs evenly, and is then transferred in 200ml hydrothermal synthesis kettle, and 200 DEG C of crystallization 30h are warming up under stirring.After crystallization,
Cooling, centrifuge separation solid product.Solid product is washed with deionized and is placed in Muffle furnace after drying at 120 DEG C to neutrality
In 600 DEG C of roasting 4h, obtain the SAPO molecular sieve sample (c) that can be used as crystal seed.Characterizing through XRD proves that the sample is SAPO-34
Molecular sieve pure phase, the partial size that SEM measures product is 5 μm or so.
Sample (d)
16.7g aluminium isopropoxide, 22g phosphoric acid, 9.6g ethyl orthosilicate, 34.5g diethylamine and 93.4g water are added into beaker
It is mixed and stirred for uniformly, being then transferred in 200ml hydrothermal synthesis kettle, 210 DEG C of crystallization 48h being warming up under stirring.Crystallization terminates
Afterwards, cooling, centrifuge separation solid product.Solid product is washed with deionized to neutrality, obtains SAPO points that can be used as crystal seed
Son sieve sample (d).Characterizing through XRD proves that the sample is SAPO-34 molecular sieve pure phase, and the partial size that SEM measures product is 8 μm of left sides
It is right.
Sample (e)
27.9g Aluminum sol, 20.5g phosphoric acid, 5.1g silica solution, 31.9g morpholine, 15.1g tetraethyl hydrogen are added into beaker
Amine-oxides and 36g water are mixed and stirred for uniformly, being then transferred in 200ml hydrothermal synthesis kettle, and 180 DEG C of crystallization are warming up under stirring
36h.After crystallization, cooling, centrifuge separation solid product, and collect mother liquor.Solid product is washed with deionized to neutrality,
After drying at 120 DEG C, the SAPO molecular sieve sample (e) that can be used as crystal seed is obtained.Characterizing through XRD proves that the sample is SAPO-
34 molecular sieve pure phases, the partial size that SEM measures product is 1 μm or so.
Sample (f)
14.9g boehmite is added into beaker, 29.9g phosphoric acid, 3.8g silica solution, 35.5g triethylamine and 87g water are mixed
Merging stirs evenly, and is then transferred in 200ml hydrothermal synthesis kettle, and 190 DEG C of crystallization 28h are warming up under stirring.After crystallization,
Cooling, centrifuge separation solid product, and collect mother liquor.Solid product is washed with deionized to neutrality, obtains can be used as crystal seed
SAPO molecular sieve sample (f).Characterizing through XRD proves that the sample is the mixture of SAPO-5 and SAPO-34 molecular sieve, and SEM is surveyed
The partial size for obtaining product is 4 μm or so.
Sample (g)
13.6g boehmite, 21g phosphoric acid, 13.2g ethyl orthosilicate, 27.3g N, N-diisopropyl are added into beaker
Ethamine and 82.1g water are mixed and stirred for uniformly, being then transferred in 200ml hydrothermal synthesis kettle, and 175 DEG C of crystallization are warming up under stirring
24h.After crystallization, cooling, centrifuge separation solid product, and collect mother liquor.Solid product is washed with deionized to neutrality,
After being dried at 120 DEG C, 550 DEG C of roasting 6h in Muffle furnace are placed in, the SAPO molecular sieve sample (g) that can be used as crystal seed is obtained.Through
XRD characterization proves that the sample is SAPO-18 molecular sieve pure phase, and the partial size that SEM measures product is 3 μm or so.
Sample (h)
17.8g aluminium isopropoxide, 20.9g phosphoric acid, 11.5g ethyl orthosilicate, 11.3g hexamethylene imine are added into beaker
It is mixed and stirred for uniformly, being then transferred in 200ml hydrothermal synthesis kettle with 65g water, 200 DEG C of crystallization is warming up under stirring for 24 hours.It is brilliant
After change, cooling, centrifuge separation solid product.Solid product is washed with deionized to neutrality, after being dried at 120 DEG C,
Obtain can be used as the SAPO molecular sieve sample (h) of crystal seed.Characterizing through XRD proves that the sample is SAPO-35 molecular sieve pure phase, SEM
The partial size for measuring product is 8 μm or so.
Sample is (i)
14.9g boehmite, 21.9g phosphoric acid, 8.5g silica solution, 12.4g cyclohexylamine and 93.9g water are added into beaker
It is mixed and stirred for uniformly, being then transferred in 200ml hydrothermal synthesis kettle, 180 DEG C of crystallization 72h being warming up under stirring.Crystallization terminates
Afterwards, cooling, centrifuge separation solid product.Solid product is washed with deionized to neutrality, after drying at 120 DEG C, obtaining can
SAPO molecular sieve sample as crystal seed is (i).Characterizing through XRD proves that the sample is SAPO-44 molecular sieve pure phase, and SEM measures production
The partial size of product is 7 μm or so.
Sample (j)
23.9g boehmite is added into beaker, 36.9g phosphoric acid, 26g triethylamine and 58.8g water are mixed and stirred for
It is even, it is then transferred in 200ml hydrothermal synthesis kettle, 170 DEG C of crystallization 48h is warming up under stirring.After crystallization, cooling, centrifugation
Solid product is separated, and collects mother liquor.Solid product is washed with deionized and is placed in Muffle after drying at 120 DEG C to neutrality
550 DEG C of roasting 6h, obtain the AlPO4 sieve sample (j) that can be used as crystal seed in furnace.Characterizing through XRD proves that the sample is
AlPO4-5 molecular sieve pure phase, the partial size that SEM measures product is 2~10 μm.
Sample (k)
11.5g boehmite, 18.6g phosphoric acid, 9.8g silica solution, 23.4g triethylamine, 1.2g nitric acid are added into beaker
Nickel and 89.8g water are mixed and stirred for uniformly, being then transferred in 200ml hydrothermal synthesis kettle, and 190 DEG C of crystallization are warming up under stirring
30h.After crystallization, cooling, centrifuge separation solid product.Solid product is washed with deionized to neutrality, is dried at 120 DEG C
After dry, 550 DEG C of roasting 6h in Muffle furnace are placed in, the SAPO molecular sieve sample (g) that can be used as crystal seed is obtained.Characterizing through XRD proves
The sample is NiAPSO-34 molecular sieve pure phase, and the partial size that SEM measures product is 4 μm or so.
Sample (l)
11g boehmite, 21.4g phosphoric acid, 11.5g diisopropylamine, 0.42g zinc nitrate and 86.2g water are added into beaker
It is mixed and stirred for uniformly, being then transferred in 200ml hydrothermal synthesis kettle, 175 DEG C of crystallization 40h being warming up under stirring.Crystallization terminates
Afterwards, cooling, centrifuge separation solid product, and collect mother liquor.Solid product is washed with deionized to neutrality, obtains can be used as crystalline substance
The AlPO4 sieve sample (l) of kind.Characterizing through XRD proves that the sample is ZnAPO4-11 molecular sieve pure phase, and SEM measures product
Partial size be 3~10 μm.
Embodiment 2~15: the preparation of small particle aluminium phosphate molecular sieve
By silicon source, silicon source, phosphorus source, phosphate aluminium molecular sieve (a)~(l) that can be used as crystal seed, metal salt solution, organic amine template R
Silicon source, silicon source, phosphorus source, the phosphorus aluminium point that can be used as crystal seed are equipped with mother liquor collected when water or above-mentioned preparation (a)~(l) sample
Son sieve (a)~(l), metal salt solution, organic amine template R are mixed in a certain ratio obtained crystallization liquid, and at a certain temperature two
Secondary crystallization is for a period of time；The aluminium phosphate molecular sieve of small particle is prepared into through separating.The wherein source as the crystal seed of raw material and biography
Template that system/crystal seed method secondary crystallization uses, each raw material, raw material proportioning (molar ratio), tradition/crystal seed method secondary crystallization temperature
The grain size comparison of degree and time, two methods products obtained therefrom are shown in Table shown in 1.
Table 1
Claims (5)
1. a kind of method for reducing zeolite crystal partial size, preparation process include:
(1) by silicon source, silicon source, phosphorus source, the phosphate aluminium molecular sieve that can be used as crystal seed, metal salt solution, water or the crystalline substance after crystal seed is prepared
Change mother liquor to be uniformly mixed, is then mixed to prepare Primogel crystallization liquid I with organic amine template R；Each component rubs in crystallization liquid I
Your proportion is as follows: SiO2 : Al2O3 : P2O5 : R : H2O: Me=(0~2): (0~2): (0~2): (0.1~
20): (0~100): (0~1.5), and when water is 0, it must be used in raw material and prepare the crystallization mother liquor after crystal seed；
(2) aging 0~for 24 hours at room temperature~140 DEG C, the crystallization liquid II after obtaining aging by initial crystallization liquid I；
(3) by the crystallization liquid II after aging at 140~220 DEG C 2~40h of hydrothermal crystallizing, crystallization temperature is at least compared with aging temperature
It is 20 DEG C high；
(4) after crystallization, small crystal grain molecular sieve is obtained through cooling, washing, drying, roasting.
2. the method according to claim 1, wherein described (silicon) phosphate aluminium molecular sieve that can be used as crystal seed is selected from
SAPO-5, SAPO-11, SAPO-18, SAPO-34, SAPO-35, SAPO-44, MeAPSO and AlPO4-5, AlPO4-11 and
One or more of MeAPO4.
3. the method according to claim 1, wherein the silicon source is selected from silica solution, ethyl orthosilicate, activity two
The mixing of one or more of silica, the kaolin through overactivation or the gangue through overactivation；Source of aluminium is selected from thin
One or more of diaspore, boehmite, Aluminum sol, aluminium oxide, aluminium hydroxide, aluminum soluble salt or aluminium isopropoxide
Mixing；Phosphorus source is selected from the mixing of one or more of phosphoric acid, phosphorous acid, phosphorus pentoxide；The template is selected from two
Ethamine, triethylamine, morpholine, tetraethyl ammonium hydroxide, hexamethylene imine, N, N- diisopropylethylamine, cyclohexylamine, diisopropyl
The mixing of one or more of amine, di-n-propylamine or Tri-n-Propylamine, and the organic amine template R is not preferably tetraethyl hydrogen
Amine-oxides；The metal salt is selected from the mixing of one or more of the nitrate of metal, sulfate, acetate, chloro salt, should
Metal salt is soluble easily in water.
4. the method according to claim 1, wherein (silicon) phosphate aluminium molecular sieve that can be used as crystal seed and initial
The mass ratio of gel crystallization liquid is 0.03~0.3: 1.
5. the method according to claim 1, wherein being synthesized using molecular sieve made from this method compared with conventional hydrothermal
Molecular sieve made from method, at least in one dimension crystal particle diameter reduce 50% or more, wherein the small particle molecular sieve be selected from
SAPO-5, SAPO-11, SAPO-18, SAPO-34, SAPO-35, SAPO-44, MeAPSO and AlPO4-5, AlPO4-11 and
One or more of MeAPO4.
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