CN107128944A - A kind of preparation method and applications of SAPO-11 molecular sieves - Google Patents
A kind of preparation method and applications of SAPO-11 molecular sieves Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 45
- 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 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 61
- 230000008025 crystallization Effects 0.000 claims abstract description 61
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 230000032683 aging Effects 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010457 zeolite Substances 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 229910052681 coesite Inorganic materials 0.000 claims description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 229910052682 stishovite Inorganic materials 0.000 claims description 19
- 229910052905 tridymite Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 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 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009415 formwork Methods 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000007787 solid Substances 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
- 229940043279 diisopropylamine Drugs 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 7
- 241000269350 Anura Species 0.000 abstract 4
- 238000003756 stirring Methods 0.000 description 17
- 238000010792 warming Methods 0.000 description 17
- 239000003643 water by type Substances 0.000 description 16
- 241000196324 Embryophyta Species 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- -1 alkyl silane quaternary ammonium salt Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical class CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- 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]
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—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)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a kind of preparation method of the molecular sieves of SAPO 11, comprise the following steps：1) water, phosphorus source, silicon source, silicon source and template are mixed, obtains colloidal mixture；2) by step 1) obtained colloidal mixture aging under certain mixing speed, obtain gel；3) by step 2) the obtained gel after crystallization, through being filtered, washed and dried drying, obtains the zeolite products of SAPO 11 under certain mixing speed.The methods described provided according to the present invention, can effectively shorten the crystallization process time, substantially reduce the generation of stray crystal, obtain the evengranular molecular sieve crystals of SAPO 11.Application present invention also offers the molecular sieves of SAPO 11 prepared according to methods described and its in the reaction of isomerisation of olefin, alkane isomerization and isomerization dewaxing.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of preparation method and applications of SAPO-11 molecular sieves.
Background technology
Aluminium silicophosphate molecular sieve SAPO-11 skeleton is made up of Si, P, Al and O element, and its structure belongs to state
Border zeolite association is named as AEL type structures.SAPO-11 molecular sieves have one-dimensional ten-ring channel system, hole
Road is ellipse, freely a diameter of 0.65 × 0.40 nanometer, belongs to rhombic system, unit cell dimension is received for a=1.35
Rice, b=1.85 nanometers, c=0.84 nanometers.Due to there is Si-O-Al in the skeleton structure of SAPO-11 molecular sieves
Connection, so the molecular sieve has acidity.At present, SAPO-11 molecular sieves catalytic cracking, be hydrocracked,
A variety of oil refining and the chemical engineering industries such as isomerization, the alkylation with side chain aromatic hydrocarbons, isomerization dewaxing and light olefin polymerization
In widely studied or applied.
SAPO-11 molecular sieves are generally prepared using the method for Hydrothermal Synthesiss.Common step is to intend thin water
Aluminium stone is silicon source, and phosphoric acid is phosphorus source, and tetraethyl orthosilicate or acidic silicasol are silicon source, by certain suitable
Sequence mixes, stirred, and adds template di-n-propyl amine and stirs, then inserts in Hydrothermal Synthesiss kettle,
At a certain temperature crystallization and obtain.US4440871 first reported the synthesis side of SAPO-11 molecular sieves
Method.Then there are many reports on SAPO-11 Zeolite synthesis methods again.CN102372289 uses two
Ethamine and hydrofluoric acid are mixed templates, synthesize the little crystal grain SAPO-11 molecular sieves with AEL structure
Preparation method.CN101913621 is used as SAPO-11 using long chain alkyl silane and long chain alkyl silane quaternary ammonium salt
The silicon source of molecular sieve, synthesizes the SAPO-11 molecular sieves by assembling compared with little crystal grain, the molecular sieve have compared with
Big outer surface and mesopore volume.
Lot of documents is studied hydro-thermal method synthesis SAPO-11 from different perspectives, is concentrated mainly on feed stock
The influence that matter and proportioning, template, modification and crystallization condition etc. are synthesized to SAPO-11.SAPO-11
The preparation process of molecular sieve is divided into two processes of aging and crystallization, generally selects and either statically or dynamically operates, but static
Crystallization is readily obtained larger nucleus (such as about 5 μm of granularity), and the time of dynamic crystallization often longer (example
Such as larger than 72h)；And in the amplification production process of SAPO-11 molecular sieves, synthesis is generally carried out under agitation.
However, prior art not to mixing speed in aging and crystallization process to prepare SAPO-11 generation influence
Studied, therefore exist that crystallization time is longer, crystallinity is low, particle is uneven, easily stray crystal etc. occur and ask
Topic.
The content of the invention
To solve the problem of prior art is present, the invention provides a kind of preparation method of SAPO-11 molecular sieves.
The present invention is by using speed change whipping process so that the mixing speed of the ageing process of SAPO-11 molecular sieves is higher than
The mixing speed of crystallization process, and by optimizing the mixing speed of aging and crystallization process, obtain crystallinity it is high,
Evengranular SAPO-11 molecular sieves, and shorten crystallization time.
The invention provides a kind of preparation method of SAPO-11 molecular sieves, comprise the following steps：
1) water, phosphorus source, silicon source, silicon source and template are mixed, obtains colloidal mixture；
2) by step 1) obtained colloidal mixture aging under certain mixing speed, obtain gel；
3) by step 2) the obtained gel is under certain mixing speed after crystallization, through filtering, washing and dry
It is dry, obtain SAPO-11 zeolite products.
In certain embodiments of the present invention, in step 1) in, the mol ratio of source of aluminium and silicon source is with Al2O3:
SiO2Meter is preferably 1:(0.06-0.6).Under low whipping speed of the present invention, crystallization temperature and the synergy of time,
The generation of stray crystal can be avoided in the molar ratio range of source of aluminium and silicon source, preparation condition is gentle, with wide
General application prospect.And prior art is in the molar ratio range, it is typically easy to produce stray crystal, or causes point
Son sieve distribution of particles is uneven.
According to the present invention, in step 1) in, source of aluminium, phosphorus source, silicon source, the mol ratio of template and water
With Al2O3:P2O5:SiO2:R:H2O meters are preferably 1.0:(0.5-1.5):(0.06-0.6):(0.5-2.0):
(30-100), more preferably 1.0:(0.8-1.3):(0.1-0.4):(0.8-1.5):(50-100), wherein R
For template.
In a preferred embodiment of the present invention, source of aluminium, phosphorus source, silicon source, template and water rub
That ratio is with Al2O3:P2O5:SiO2:R:H2O meters are preferably 1.0:1.2:0.2:1.0:80, wherein R are two just
Propyl group amine.
Mix, can obtain in the present invention, it is preferred to which silicon source, phosphorus source, silicon source and template are sequentially added in water
Obtain colloidal mixture evenly.Source of aluminium, phosphorus source, silicon source and template are commonly used in the art.
Source of aluminium preferably includes at least one of aluminium hydroxide, boehmite and aluminium isopropoxide.Phosphorus source is excellent
Choosing includes phosphoric acid and/or phosphorous acid.The silicon source preferably includes White Carbon black, tetraethyl orthosilicate, solid silicone and silicon
At least one of colloidal sol.The template is preferably organic formwork agent, more preferably including di-n-propyl amine, two
At least one of isopropylamine and diethylamide.
In a preferred embodiment of the present invention, source of aluminium is preferably boehmite, and phosphorus source is excellent
Elect phosphoric acid as, the silicon source is preferably Ludox, and the template is preferably di-n-propyl amine.
In step 1) in, the temperature of the mixing is preferably 5-60 DEG C, more preferably 10-50 DEG C, most preferably 30-40 DEG C.
It is preferred that above-mentioned each component is mixed under conditions of quickly stirring such as 100-130r/min, result in more
Good mixed effect.
According to the present invention, in step 2) in, the temperature of the aging is preferably 80-150 DEG C, more preferably
100-150℃.The time of the aging is preferably 2-8 hours, more preferably 3-5 hours.
In step 2) in, the mixing speed is preferably 200-400r/min, more preferably 220-370r/min, most
It is preferred that 220-280r/min.Within this range, the present invention results in more preferable aging effect, is conducive to shortening
Crystallization time, and small, scattered nucleus can be formed.
According to the present invention, in step 3) in, the temperature of the crystallization is preferably 160-230 DEG C, more preferably
190-210℃.The time of the crystallization is preferably 10-40 hours, more preferably 20-30 hours.
In a preferred embodiment of the invention, the crystallization is preferably hydrothermal crystallizing, and the pressure of the crystallization is excellent
Elect self-generated pressure as, i.e., pressure produced during hydrothermal crystallizing is carried out in closed container.
In step 3) in, the mixing speed is preferably 80-150r/min, more preferably 100-130r/min.
In the range of currently preferred crystallization mixing speed, stray crystal shape can be reduced while crystallization time is shortened
Into, and obtain the SAPO-11 molecular sieve crystals that particle is small, be evenly distributed.
In the crystallization process of the present invention, when using the quick stirring for being more than 150r/min, SAPO-11 can be extended
Crystallization time, and can cause that crystal grain is too small and size distribution is irregular, while making SAPO-11 filtration washings
It is difficult.When using when mixing slowly of 80r/min is less than, making material mixing uneven again, the nucleus of formation compared with
It is few, so as to cause crystallization rate slow and stray crystal easily occur.
Further, in the range of currently preferred crystallization mixing speed, it can form finely dispersed big
Measure small nucleus, crystal is difficult aggregation in growth course, thus formed particle it is uniform, in rectangular-shape
Crystal, improves the specific surface area of SAPO-11 molecular sieves.
The present invention by each component and its certain content, and the specified temp of aging and crystallization process, the time and
The synergy of mixing speed, both ensure that each component of SAPO-11 molecular sieve gels was mixed in ageing process
Uniformly, promote silicon source dissolving and and silicon source combination, shorten the nucleation period, form more small nucleus, keep away
Exempt from the generation of stray crystal；The crystallization time of SAPO-11 molecular sieves can be shortened again, make the even particle size to be formed,
Beneficial to filtering and washing.
In the preferred embodiment of the present invention, in step 3) after the completion of crystallization, can also be by the further mistake of product
Filter, washing and dry, removing template and other impurities, obtain the higher zeolite product of purity.The mistake
Filter, wash and dry and use laboratory facilities and condition commonly used in the art, for example, dry and preferably exist
100-150 DEG C dry 1-2 hours, and roasting is preferably 500-600 DEG C and is calcined 5-8 hours.
A kind of SAPO-11 molecular sieves with AEL structure can be obtained according to the preparation method that the present invention is provided.
The molecular sieve is preferably in rectangular-shape, a length of 0.2-2 microns, a width of 0.1-0.5 microns, and thickness is 0.1-0.2
Micron.In the present invention, term " AEL structure " be skilled artisans appreciate that known AEL
Structure.SAPO-11 molecular sieves prepared by the present invention confirm as SAPO-11 molecules by X-ray diffraction spectrogram
Sieve, in 2 θ=8.12 °, 9.42 °, 13.18 °, 15.68 °, 20.46 °, 21.04 °, 22.14 °, 22.66 ° and 23.18 °
Place occurs in that the SAPO-11 characteristic diffraction peak consistent with document report.Illustrate SAPO-11 prepared by the present invention
Molecular sieve has good crystallinity and crystal structure.
Present invention also offers the SAPO-11 molecular sieves that will be prepared according to methods described isomerisation of olefin,
Application in alkane isomerization and isomerization dewaxing reaction.The SAPO-11 molecular sieves have very as catalyst
High catalytic selectivity and activity, and filter opening is not easily blocked in use, it is easy to recycle, with wide
General prospects for commercial application.
In summary, the present invention has advantages below compared with prior art：
1st, by optimizing the mixing speed of aging and crystallization process, it is uniformly dispersed, that particle is small is rectangular
Body shape SAPO-11 molecular sieves；
2nd, the method provided according to the present invention shortens 1/2-1/3 crystallization time compared with prior art.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of SAPO-11 zeolite products prepared by embodiment 1.Its
In, abscissa is the θ of angle 2 (unit °), and ordinate is the intensity (unit a.u.) of diffraction maximum.Can from Fig. 1
To find out, product 2 θ=8.12 °, 9.42 °, 13.18 °, 15.68 °, 20.46 °, 21.04 °, 22.14 °, 22.66 °
With 23.18 ° of characteristic diffraction peaks with SAPO-11 molecular sieves.
Fig. 2 is ESEM (SEM) figure of SAPO-11 zeolite products prepared by embodiment 1.It can see
The product for going out the preparation of embodiment 1 is in rectangular-shape, and uniform particle sizes are a length of 0.2-2 microns, and a width of 0.1-0.5 is micro-
Rice, and thickness are 0.1-0.2 microns.
Embodiment
The present invention will be more fully described by the following example the present invention, those skilled in the art can be more fully understood
The present invention, but these embodiments do not constitute any limitation to the scope of the present invention.
X-ray diffraction (XRD) figure is using Dutch PANalytical EMPYREAN (sharp shadow series 2) X-ray
Diffractometer is determined, using Cu K α as radiation source, x-ray tube voltage 40kV, electric current 40mA, scanning range
5-50,2 °/min of sweep speed.
ESEM (SEM) figure uses the S440 ESEMs that Leica Cambridge LTD companies produce
Determine.
The product and standard specimen that relative crystallinity obtains for each embodiment and comparative example are in XRD diffraction maximums
2 θ=8.12 °, 9.42 °, 13.18 °, 15.68 °, 20.46 °, 21.04 °, 22.14 °, 22.66 ° and 23.18 ° of diffraction
The ratio of the peak height sum at peak, the samples state for herein obtaining embodiment 1 is that (relative crystallinity is standard specimen
100%).
Embodiment 1
139.3g boehmites (are contained into 70wt%Al at room temperature2O3, purchased from Shandong Aluminum Plant) stirred
It is added in 800mL deionized waters, is then slowly added into 264.5g phosphoric acid solutions (containing phosphoric acid 85wt%),
Stir, add 45.9g Ludox (containing 25wt%SiO2), afterwards add 96.8g di-n-propyl amines and
426mL deionized waters, are again stirring for uniform.Gained mixture is transferred in dynamic high-pressure reactor, stirred
Speed is set to 350r/min, is warming up to 130 DEG C, constant temperature aging 4 hours.After aging terminates, mixing speed is set
For 140r/min, 200 DEG C are warming up to, at autogenous pressures crystallization 36 hours.After the completion of crystallization, crystallization is produced
Thing is filtered, washing, 120 DEG C of dryings, and 540 DEG C are calcined 6 hours, obtain SiO2/Al2O3Mol ratio=0.2,
The uniform SAPO-11 sieve samples of grain, relative crystallinity 100%.
Embodiment 2
139.3g boehmites (are contained into 70wt%Al at room temperature2O3, purchased from Shandong Aluminum Plant) stirred
It is added in 800mL deionized waters, is then slowly added into 264.5g phosphoric acid solutions (containing phosphoric acid 85wt%),
Stir, add 45.9g Ludox (containing 25wt%SiO2), afterwards add 96.8g di-n-propyl amines and
426mL deionized waters, are again stirring for uniform.Gained mixture is transferred in dynamic high-pressure reactor, stirred
Speed is set to 320r/min, is warming up to 130 DEG C, constant temperature aging 4 hours.After aging terminates, mixing speed is set
For 120r/min, 200 DEG C are warming up to, at autogenous pressures crystallization 24 hours.After the completion of crystallization, crystallization is produced
Thing is filtered, washing, 120 DEG C of dryings, and 540 DEG C are calcined 6 hours, obtain SiO2/Al2O3Mol ratio=0.2,
The uniform SAPO-11 sieve samples of grain, relative crystallinity 96%.
Embodiment 3
204.9g boehmites (are contained into 70wt%Al at room temperature2O3, purchased from Shandong Aluminum Plant) stirred
It is added in 800mL deionized waters, is then slowly added into 389.0g phosphoric acid solutions (containing phosphoric acid 85wt%),
Stir, add 67.48g Ludox (containing 25wt%SiO2), 142.3g di-n-propyl amines are added afterwards
With 294.9mL deionized waters, it is again stirring for uniform.Gained mixture is transferred in dynamic high-pressure reactor,
Mixing speed is set to 300r/min, is warming up to 130 DEG C, constant temperature aging 4 hours.After aging terminates, stirring speed
Degree is set to 120r/min, is warming up to 200 DEG C, at autogenous pressures crystallization 30 hours.After the completion of crystallization, by crystalline substance
Change product filtering, wash, 120 DEG C of dryings, 540 DEG C are calcined 6 hours, obtain SiO2/Al2O3Mol ratio=0.2,
Evengranular SAPO-11 sieve samples, relative crystallinity 98%.
Embodiment 4
139.3g boehmites (are contained into 70wt%Al at room temperature2O3, purchased from Shandong Aluminum Plant) stirred
It is added in 800mL deionized waters, is then slowly added into 264.5g phosphoric acid solutions (containing phosphoric acid 85wt%),
Stir, add 91.8g Ludox (containing 25wt%SiO2), afterwards add 96.8g di-n-propyl amines and
418mL deionized waters, are again stirring for uniform.Gained mixture is transferred in dynamic high-pressure reactor, stirred
Speed is set to 350r/min, is warming up to 130 DEG C, constant temperature aging 4 hours.After aging terminates, mixing speed is set
For 140r/min, 200 DEG C are warming up to, at autogenous pressures crystallization 24 hours.After the completion of crystallization, crystallization is produced
Thing is filtered, washing, 120 DEG C of dryings, and 540 DEG C are calcined 6 hours, obtain SiO2/Al2O3Mol ratio=0.4,
The uniform SAPO-11 sieve samples of grain, relative crystallinity 97%.
Embodiment 5
139.3g boehmites (are contained into 70wt%Al at room temperature2O3, Shandong Aluminum Plant) and stirred addition
Into 800mL deionized waters, 264.5g phosphoric acid solutions (containing phosphoric acid 85wt%) are then slowly added into, are stirred
Uniformly, 137.7g Ludox is added (containing 25wt%SiO2), afterwards add 96.8g di-n-propyl amines and
391.9mL deionized waters, are again stirring for uniform.Gained mixture is transferred in dynamic high-pressure reactor, stirred
Mix speed and be set to 350r/min, be warming up to 130 DEG C, constant temperature aging 4 hours.After aging terminates, mixing speed
140r/min is set to, 200 DEG C are warming up to, at autogenous pressures crystallization 24 hours.After the completion of crystallization, by crystallization
Product is filtered, washing, 120 DEG C of dryings, and 540 DEG C are calcined 6 hours, obtain SiO2/Al2O3Mol ratio=0.6,
Evengranular SAPO-11 sieve samples, relative crystallinity 97%.
Embodiment 6
At room temperature by 78.0g aluminium hydroxides, 114.0g phosphoric acid solutions (containing phosphoric acid 85wt%), the positive silicon of 41.6g
Acetoacetic ester and 146.0g diisopropylamines are added in 800mL deionized waters, are stirred.It is mixed by what is obtained
Compound is transferred in dynamic high-pressure reactor, and mixing speed is set to 250r/min, is warming up to 100 DEG C, constant temperature is old
Change 3 hours.After aging terminates, mixing speed is set to 100r/min, is warming up to 180 DEG C, at autogenous pressures
Crystallization 30 hours.After the completion of crystallization, crystallization product is filtered, washed, 120 DEG C of dry hours, 540 DEG C of roastings
Burn 6 hours, obtain SiO2/Al2O3Mol ratio=0.2, evengranular SAPO-11 sieve samples, relatively
Crystallinity 95%.
Comparative example 1
139.3g boehmites (are contained into 70wt%Al at room temperature2O3, purchased from Shandong Aluminum Plant) stirred
It is added in 800mL deionized waters, is then slowly added into 264.5g phosphoric acid solutions (containing phosphoric acid 85wt%),
Stir, add 45.9g Ludox (containing 25wt%SiO2), afterwards add 96.8g di-n-propyl amines and
426mL deionized waters, are again stirring for uniform.Gained mixture is transferred in dynamic high-pressure reactor, heated up
To 130 DEG C, constant temperature stands aging 4 hours.After aging terminates, 200 DEG C are warming up to, it is quiet at autogenous pressures
Put crystallization 36 hours.After the completion of crystallization, crystallization product is filtered, washed, 120 DEG C of dry hours, 540 DEG C
Roasting 6 hours, obtains containing SAPO-31, unequigranular and mixed molecular sieve sample of the granularity more than 3 μm
Product, SAPO-11 molecular sieves, relative crystallinity 80%.
Comparative example 2
139.3g boehmites (are contained into 70wt%Al at room temperature2O3, purchased from Shandong Aluminum Plant) stirred
It is added in 800mL deionized waters, is then slowly added into 264.5g phosphoric acid solutions (containing phosphoric acid 85wt%),
Stir, add 45.9g Ludox (containing 25wt%SiO2), 96.8g di-n-propyl amines are added afterwards
With 426mL deionized waters, it is again stirring for uniform.Gained mixture is transferred in dynamic high-pressure reactor, stirred
Mix speed and be set to 450r/min, be warming up to 130 DEG C, constant temperature aging 4 hours.After aging terminates, mixing speed
50r/min is set to, 200 DEG C are warming up to, at autogenous pressures crystallization 36 hours.After the completion of crystallization, by crystallization
Product is filtered, washing, 120 DEG C of dryings, and 540 DEG C are calcined 6 hours, obtains unequigranular and granularity is more than 3 μm
SAPO-11 sieve samples, relative crystallinity 85%.
Comparative example 3
At room temperature by 78.0g aluminium hydroxides, 114.0g phosphoric acid solutions (containing phosphoric acid 85wt%), the positive silicon of 41.6g
Acetoacetic ester and 146.0g diethylamides are added in 800mL deionized waters, are stirred.By obtained mixing
Thing is transferred in dynamic high-pressure reactor, and mixing speed is set to 450r/min, is warming up to 100 DEG C, constant temperature aging 3
Hour.After aging terminates, mixing speed is set to 50r/min, is warming up to 180 DEG C, at autogenous pressures crystallization 60
Hour.After the completion of crystallization, crystallization product is filtered, washed, 120 DEG C of dry hours, 540 DEG C are calcined 6 hours,
Obtain SiO2/Al2O3The SAPO-11 sieve samples of mol ratio=0.2, relative crystallinity 90%.
Determined through X-ray diffraction and ESEM, sieve sample prepared by embodiment 2-6 is made with embodiment 1
Standby sample has essentially identical characteristic diffraction peak and crystal habit.
In the range of embodiment and comparative example, the aging limited in the present invention and the mixing speed of crystallization process,
The crystallization process time (for example shortening to 30h from more than 60h) can be shortened, the generation of stray crystal is reduced, obtain
Single SAPO-11 molecular sieve crystallites.Also, obtained molecular sieve crystal in rectangular-shape, be uniformly dispersed and
Surface is neat, can effectively improve the catalytic performance of SAPO-11 molecular sieves.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit of the invention and model
Modification in enclosing will be apparent.However, it should be understood that each side, difference that the present invention is recorded
The each several part of embodiment and the various features enumerated can be combined or all or part of exchange.Above-mentioned
Each embodiment in, those with reference to another embodiment embodiment can suitably with its
Its embodiment is combined, and this is will be to understand by those skilled in the art.In addition, those skilled in the art
It will be understood that, description above is only the mode of example, it is no intended to the limitation present invention.
Claims (10)
1. a kind of preparation method of SAPO-11 molecular sieves, comprises the following steps：
1) water, phosphorus source, silicon source, silicon source and template are mixed, obtains colloidal mixture；
2) by step 1) obtained colloidal mixture aging under certain mixing speed, obtain gel；
3) by step 2) the obtained gel is under certain mixing speed after crystallization, through filtering, washing and dry
It is dry, obtain SAPO-11 zeolite products.
2. according to the method described in claim 1, it is characterised in that in step 1), source of aluminium and silicon
The mol ratio in source is with Al2O3:SiO2It is calculated as 1:(0.06-0.6).
3. method according to claim 1 or 2, it is characterised in that in step 1) in, source of aluminium,
Phosphorus source, silicon source, the mol ratio of template and water are with Al2O3:P2O5:SiO2:R:H2O is calculated as 1:(0.5-1.5):
(0.06-0.6):(0.5-2.0):(30-100), preferably 1:(0.8-1.3):(0.1-0.4):(0.8-1.5):
(50-100), wherein R are template.
4. the method according to claim 1-3 any one, it is characterised in that in step 1) in, institute
Stating silicon source includes at least one of aluminium hydroxide, boehmite and aluminium isopropoxide；Phosphorus source includes phosphoric acid
And/or phosphorous acid；The silicon source includes at least one in White Carbon black, tetraethyl orthosilicate, solid silicone and Ludox
Kind；The template is organic formwork agent, is preferably included in di-n-propyl amine, diisopropylamine and diethylamide
At least one.
5. the method according to claim 1-4 any one, it is characterised in that in step 2) in, institute
The temperature for stating aging is 80-150 DEG C, preferably 100-150 DEG C；The time of the aging is 2-8 hours, preferably
3-5 hours.
6. the method according to claim 1-5 any one, it is characterised in that in step 2) in, institute
Mixing speed is stated for 200-400r/min, more preferably preferably 220-370r/min, 220-280r/min.
7. the method according to claim 1-6 any one, it is characterised in that in step 3) in, institute
The temperature for stating crystallization is 160-230 DEG C, preferably 190-210 DEG C；The time of the crystallization is 10-40 hours, excellent
Select 20-30 hours.
8. the method according to claim 1-7 any one, it is characterised in that in step 3) in, institute
Mixing speed is stated for 80-150r/min, preferably 100-130r/min.
9. SAPO-11 molecular sieves prepared by the method according to claim 1-8 any one, preferably described
Molecular sieve is in rectangular-shape, a length of 0.2-2 microns, a width of 0.1-0.5 microns, and thickness is 0.1-0.2 microns.
10. the SAPO-11 molecular sieves that are prepared according to any one methods described in claim 1-8 or such as
SAPO-11 molecular sieves described in claim 9 are in the reaction of isomerisation of olefin, alkane isomerization and isomerization dewaxing
Application.
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| CN112209405A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve and synthetic method and application thereof |
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| CN102530988A (en) * | 2010-12-20 | 2012-07-04 | 中国石油化工股份有限公司 | Method for preparing SAPO-11 molecular sieve and application of SAPO-11 molecular sieve |
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| Title |
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| 刘艳惠等: "不同晶化方式对SAPO－11分子筛的物化性质的影响", 《现代化工》 * |
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| CN109879296A (en) * | 2019-04-02 | 2019-06-14 | 中国科学院上海高等研究院 | The preparation method and application of monocrystalline SAPO-11 molecular sieve, hydroisomerization catalyst |
| CN109879296B (en) * | 2019-04-02 | 2022-07-08 | 中国科学院上海高等研究院 | Preparation method and application of single crystal SAPO-11 molecular sieve and hydroisomerization catalyst |
| CN112209405A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve and synthetic method and application thereof |
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