CN106564912B - A kind of double micropore SAPO-34/SAPO-18 composite molecular screens and its preparation method and application - Google Patents
A kind of double micropore SAPO-34/SAPO-18 composite molecular screens and its preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 127
- 230000008025 crystallization Effects 0.000 claims abstract description 127
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 239000007787 solid Substances 0.000 claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000010703 silicon Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical group CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- 229910001593 boehmite Inorganic materials 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 10
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 230000012010 growth Effects 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 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
- 239000003610 charcoal Substances 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 abstract description 51
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 51
- -1 ethylene, propylene Chemical group 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 39
- 239000003643 water by type Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to molecular sieve art, specifically provide it is a kind of preparing double micropore SAPO-34/SAPO-18 composite molecular screens and preparation method thereof, this method includes：(1) will carry out pre- crystallization for synthesizing the raw mixture A of SAPO-34 makes pre- crystallization obtain the pre- crystallization liquid S1 without solid；Pre- crystallization is made to obtain the pre- crystallization liquid S2 without solid by pre- crystallization is carried out for synthesizing the raw mixture B of SAPO-18；(2) crystallization is carried out after mixing pre- crystallization liquid S1 and pre- crystallization liquid S2, solid is isolated from crystallization liquid, is roasted after dry or not dry；And application of the double micropore SAPO-34/SAPO-18 composite molecular screens of the present invention in organic oxygen-containing compound producing light olefins.Two kinds of molecular sieve ratios of double-micropore composite molecular sieve SAPO-34/SAPO-18 of the present invention are adjustable, and in the industrial production for using it for organic oxygen-containing compound producing light olefins, ethylene, propylene ratio is adjustable in product, and the molecular sieve catalytic active of the present invention is high.
Description
Technical field
The present invention relates to a kind of preparation methods of double micropore SAPO-34/SAPO-18 composite molecular screens, and by the present invention
The obtained double micropore SAPO-34/SAPO-18 composite molecular screens of method, and the present invention double micropore SAPO-34/SAPO-18
Composite molecular screen is in organic oxygen-containing compound producing light olefins as the application of catalyst activity component.
Background technology
SAPO-34 molecular sieves are by SiO2, AlO2 -, PO2 +The microporous crystals that three kinds of tetrahedron elements are constituted, crystal knot
Structure is similar to Chabazite-type (CHA), and excellent catalytic performance is shown in reaction for preparing light olefins from methanol, but was being reacted
It is easy quickly to form carbon distribution and lead to rapid catalyst deactivation in journey.
SAPO-18 molecular sieves are a kind of AEI structure molecular screens with the microcosmic pore passage structure similar with CHA structure, by
Less in the sour position of its B acid, acid moderate, green coke rate is slower, is shown in methanol to olefins reaction higher activity stabilized
Property.
Studies have shown that the SAPO-34/SAPO-18 composite molecular screens of double microcellular structures can effectively improve the acid of molecular sieve
Property, carbon deposition rate is reduced, and then improve its catalytic performance.
CN102372291A discloses a kind of preparation method of SAPO-18/SAPO-34 coexisting molecular sieves.This method passes through
Using the template tetraethyl ammonium hydroxide for being suitble to two kinds of objects mutually to grow simultaneously, controls and the raw material in the crystallization liquid of growth is suitble to match
Than adjusting the crystallization temperature that involved object is mutually grown, synthesizing coexisting molecular sieve, crystallization temperature 150-200 under hydrothermal conditions
DEG C, crystallization time is 18-160 hours.
CN103418431A discloses a kind of preparation method of SAPO-34/SAPO-18 composite molecular screens.This method passes through
Using SAPO-18 molecular sieves as crystal seed, it is formed by colloidal solution with silicon source, phosphorus source, silicon source and template and mixes, through hydro-thermal
Crystallization obtains composite molecular screen.
Invention content
Short it is an object of the invention on the basis of existing technology, provide a kind of required crystallization time, combined coefficient is high,
Two-phase proportion is easily adjusted and the preparation method of the high double-micropore composite molecular sieve SAPO-34/SAPO-18 of catalytic activity and by the party
The double-micropore composite molecular sieve SAPO-34/SAPO-18 and its application that method obtains.
To realize foregoing purpose, according to the first aspect of the invention, double micropore SAPO- are prepared the present invention provides a kind of
The method of 34/SAPO-18 composite molecular screens, including：
(1) it will carry out pre- crystallization for synthesizing SAPO-34 raw mixture A to make that pre- crystallization is obtained without solid pre-
Crystallization liquid S1；Pre- crystallization is made to obtain the pre- crystalline substance without solid by pre- crystallization is carried out for synthesizing the raw mixture B of SAPO-18
Change liquid S2；
(2) will pre- crystallization liquid S1 and pre- crystallization liquid S2 mix after carry out crystallization, isolate solid from crystallization liquid, it is dry or
It is roasted after not dry；
Wherein, pre- crystallization is the process for the hydrothermal synthesis reaction to form SAPO-34 nucleus and SAPO-18 nucleus, and crystallization is
Make the process of SAPO-34 nucleus and SAPO-18 nucleus growths and the hydrothermal synthesis reaction grown up.
According to the second aspect of the invention, the present invention provides the double micropores obtained according to the method described in the present invention
SAPO-34/SAPO-18 composite molecular screens.
According to the third aspect of the invention we, it is multiple that the present invention provides double micropore SAPO-34/SAPO-18 of the present invention
Molecular sieve is closed in organic oxygen-containing compound producing light olefins as the application of catalyst activity component.
The present invention so that pre- crystallization is free of by the way that the raw mixture A for being used to synthesize SAPO-34 is carried out pre- crystallization
The pre- crystallization liquid S1 of solid；Pre- crystallization is obtained without solid the pre- crystallization of raw mixture B progress for synthesizing SAPO-18
The pre- crystallization liquid S2 of body, crystallization after then being mixed pre- crystallization liquid S1 with pre- crystallization liquid S2 can prepare composite effect
Good, the double-micropore composite molecular sieve SAPO-34/SAPO-18 of the performances such as pore structure, acidity, catalytic performance optimization has been used it for
In the industrial production of machine preparing low-carbon olefin from oxygen-containing compounds, ethylene, propylene ratio is adjustable in product：It can be according to ethylene, propylene
The market demand carries out the regulation and control of ethylene, propylene in product by the regulation and control of two kinds of molecular sieve ratios.
And for the method for the present invention compared with the methods of traditional crystal seed method, required crystallization time is short, and combined coefficient is high, multiple
Two-phase proportion in molecular sieve is closed easily to adjust.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is X-ray diffraction (XRD) figure of sample synthesized by embodiment 1-6 and comparative example 1-2.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, double micropore SAPO-34/SAPO-18 composite molecular screens refer in the composite molecular screen
Two-phase is existed simultaneously, such as is shown in X-ray diffraction (XRD) figure, SAPO-34 and SAPO-18 molecular sieves can be existed simultaneously
Characteristic diffraction peak, wherein the characteristic peak of SAPO-34 molecular sieves appears in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, and (20.5
± 0.1) °, (25.1 ± 0.1) ° etc., the characteristic peak of SAPO-18 molecular sieves appears in 2 θ=(9.5 ± 0.1) °, (10.4 ±
0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc..
As previously mentioned, the present invention provides a kind of method preparing double micropore SAPO-34/SAPO-18 composite molecular screens, it should
Method includes：
(1) it will carry out pre- crystallization for synthesizing SAPO-34 raw mixture A to make that pre- crystallization is obtained without solid pre-
Crystallization liquid S1；Pre- crystallization is made to obtain the pre- crystalline substance without solid by pre- crystallization is carried out for synthesizing the raw mixture B of SAPO-18
Change liquid S2；
(2) will pre- crystallization liquid S1 and pre- crystallization liquid S2 mix after carry out crystallization, isolate solid from crystallization liquid, it is dry or
It is roasted after not dry.
In the present invention, pre- crystallization is the process for the hydrothermal synthesis reaction to form SAPO-34 nucleus and SAPO-18 nucleus, brilliant
Change is to make the process of SAPO-34 nucleus and SAPO-18 nucleus growths and the hydrothermal synthesis reaction grown up.
According to the method for the present invention, the purpose of the present invention, the raw material mixing may be implemented according to preceding solution
As long as object A satisfactions can be used in synthesizing SAPO-34, for the present invention, in the preferably described raw mixture A, material rubs
You are than being aR1:bSiO2:Al2O3:cP2O5:dH2O, wherein R1 indicates template R1, a ranging from：0.1-3, b are ranging from：
0.1-1, c are ranging from：0.5-1.8, d are ranging from：20-100.
According to the method for the present invention, the purpose of the present invention, the raw material mixing may be implemented according to preceding solution
As long as object B satisfactions can be used in synthesizing SAPO-18, for the present invention, in the preferably described raw mixture B, material rubs
You are than being aR2:bSiO2:Al2O3:cP2O5:dH2O, wherein R2 indicates template R2, a ranging from：0.5-3, b are ranging from：
0.01-0.3, c are ranging from：0.6-1.5, d are ranging from：10-100.
According to the method for the present invention, as long as the pre- crystallization of raw mixture A progress for synthesizing SAPO-34 is made pre- crystalline substance
Change and obtains the pre- crystallization liquid S1 without solid, optional wider range of the condition of pre- crystallization, for the present invention, preferred raw material
The condition of the pre- crystallization of mixture A includes：Temperature is 150-210 DEG C, and it is 200 DEG C to use in embodiment；More preferable pre- crystallization
Time be 1-12h, preferably 5-10h.
According to the method for the present invention, as long as the pre- crystallization of raw mixture B progress for synthesizing SAPO-18 is made pre- crystalline substance
Change and obtains the pre- crystallization liquid S2 without solid, optional wider range of the condition of pre- crystallization, for the present invention, preferred raw material
The condition of the pre- crystallization of mixture B includes：Temperature is 150-210 DEG C, and it is 180 DEG C to use in embodiment；More preferable pre- crystallization
Time be 1-12h, preferably 9-12h.
According to the method for the present invention, the mixed proportion of pre- crystallization liquid S1 and pre- crystallization liquid S2 can be carried out according to actual needs
Selection can flexibly adjust SAPO- in double micropore SAPO-34/SAPO-18 composite molecular screens by adjusting the ratio of the two
34 with the ratios of SAPO-18 two-phases, and by traditional crystal seed method etc. can not both flexible modulations ratio, in commercial Application
In it is extremely inconvenient, this shows further where the advantage of the present invention.
According to a preferred embodiment of the present invention, the mixed weight ratio of pre- crystallization liquid S1 and pre- crystallization liquid S2 are
(0.01-100):1, preferably (0.5-10):1.
According to the method for the present invention, in step (2), optional wider range of condition of crystallization is preferably wrapped for the present invention
It includes：Temperature is 150-210 DEG C, in embodiment preferably 200 DEG C；More preferable crystallization time is 1-24 hours, more preferably
6-12 hours.
With the method for the invention it is preferred to which the raw mixture A is by silicon source A, deionized water, phosphorus source A, silicon source A and mould
It is aged and obtains after plate agent R1 mixing, wherein the condition being more preferably aged includes：Temperature is room temperature, time 1-24h.The present invention
In, mixed mode is not specially limited, and is mixed according to the ordinary skill in the art.
With the method for the invention it is preferred to which the raw mixture B is by silicon source B, deionized water, phosphorus source B, silicon source B and mould
It is aged and obtains after plate agent R2 mixing, wherein the condition being more preferably aged includes：Temperature is room temperature, time 1-24h.The present invention
In, mixed mode is not specially limited, and is mixed according to the ordinary skill in the art.
According to the method for the present invention, the present invention to the type of the silicon source A and silicon source B without particular/special requirement, for the present invention,
As long as meet be respectively prepare SAPO-34, SAPO-18 needed for silicon source, silicone grease for example, commonly used in the art, Ludox,
Silica, white carbon etc., for the present invention, the preferably described silicon source A and silicon source B each be selected from ethyl orthosilicate, Ludox and
It is one or more in white carbon.
According to the method for the present invention, the present invention to the type of source of aluminium A and silicon source B without particular/special requirement, for the present invention,
Silicon source needed for SAPO-34, SAPO-18, boehmite for example, commonly used in the art, aluminium are prepared as long as meeting and being respectively
Colloidal sol, organo-aluminium alcoholate, aluminium oxide etc., for the present invention, it is molten that preferably source of aluminium A and silicon source B each are selected from boehmite, aluminium
It is one or more in glue and aluminium isopropoxide.
According to the method for the present invention, the present invention to the type of phosphorus source A and phosphorus source B without particular/special requirement, for the present invention,
Phosphorus source needed for SAPO-34, SAPO-18 is prepared as long as meeting and being respectively, for the present invention, preferably phosphorus source A and phosphorus source B
It each is selected from phosphoric acid and/or phosphorous acid.
According to the method for the present invention, the selectable range of the type of the template R1 is wider, and commonly used in the art can
The template for being used to prepare SAPO-34 is used equally for the present invention, for the present invention, the preferably described template R1 be selected from triethylamine,
It is one or more in diethylamine, tetraethyl ammonium hydroxide, n-butylamine and morpholine.
According to the method for the present invention, the selectable range of the type of the template R2 is wider, and commonly used in the art can
The template for being used to prepare SAPO-18 is used equally for the present invention, and for the present invention, the preferably described template R2 is selected from tetraethyl hydrogen
Amine-oxides and/or N, N- diisopropylethylamine.
The present invention so that pre- crystallization is free of by the way that the raw mixture A for being used to synthesize SAPO-34 is carried out pre- crystallization
The pre- crystallization liquid S1 of solid；Pre- crystallization is obtained without solid the pre- crystallization of raw mixture B progress for synthesizing SAPO-18
The pre- crystallization liquid S2 of body, crystallization after then being mixed pre- crystallization liquid S1 with pre- crystallization liquid S2 can prepare composite effect
It is good, the double-micropore composite molecular sieve SAPO-34/SAPO-18 of the performances such as pore structure, acidity, catalytic performance optimization.
And for the method for the present invention compared with the methods of traditional crystal seed method, required crystallization time is short, and combined coefficient is high, multiple
Two-phase proportion in molecular sieve is closed easily to adjust.
The present invention provides double micropore SAPO-34/SAPO-18 composite molecular screens that the method according to the invention obtains.
The performances such as double micropore SAPO-34/SAPO-18 compound molecules sieve pore structures of the present invention, acidity, catalytic performance
It shows excellent.
The present invention also provides double micropore SAPO-34/SAPO-18 composite molecular screens of the present invention in organic oxygen-containing
Close the application as catalyst activity component in object producing light olefins.
, according to the invention it is preferred to which the organic oxygen-containing compound is methanol and/or dimethyl ether.
Double micropore SAPO-34/SAPO-18 composite molecular screens of the present invention are used for organic oxygen-containing compound low-carbon alkene
In the industrial production of hydrocarbon, ethylene, propylene ratio is adjustable in product：Two kinds of molecules can be passed through according to the market demand of ethylene, propylene
The regulation and control of sieve ratio example carry out the regulation and control of ethylene, propylene in product.
Whole process is described in detail below by embodiment, but scope of the presently claimed invention is not by this
The limitation of a little embodiments.Meanwhile embodiment has been merely given as realizing the partial condition of this purpose, but be not meant to must satisfy
These conditions can just reach this purpose.
In the present invention, XRD spectra is measured by Bruker AXS D8A X-ray diffractometers, operating voltage 40kV, electric current
40mA, 5 ° -50 ° of scanning range.
Embodiment 1
1) respectively that the boehmite of 8.22g (alumina content 62 weight %, same as below), 11.53g phosphoric acid is (dense
Spend 85 weight %) and 38.88g deionized waters be mixed, strong stirring is after 1 hour, and the silicon that solid content is 40 weight % is added dropwise
Colloidal sol 2.25g, uniformly rear addition template triethylamine (TEA) 10.12g to be mixed, continue to stir 2h, 20 DEG C of ageing 2h of room temperature；
Each component molar ratio of material is in gained raw mixture A：2TEA:0.3SiO2:Al2O3:P2O5:50H2O.By above-mentioned gel original
Material mixture A is fitted into the reaction kettle with polytetrafluoro liner, in the pre- crystallization of 200 DEG C of hydro-thermals 10 hours, obtains pre- crystallization liquid S1；
Respectively by the boehmite of 8.22g (alumina content 62 weight %, same as below), 11.53g phosphoric acid (concentration
85 weight %) and the mixing of 35.05g deionized waters, for strong stirring after 1 hour, the silicon that dropwise addition solid content is 40 weight % is molten
Glue 1.13g, uniformly rear addition template n,N-diisopropylethylamine (DIEA) 9.69g to be mixed continue stirring 2h, 20 DEG C of room temperature
It is aged 2h.Each component molar ratio of material is in gained raw mixture B：1.5DIEA:0.15SiO2:Al2O3:P2O5:45H2O.It will
Above-mentioned gel material mixture B is fitted into the reaction kettle with polytetrafluoro liner, in the pre- crystallization of 180 DEG C of hydro-thermals 10 hours, is obtained pre-
Crystallization liquid S2；
2) in mass ratio 1:1 mixes pre- crystallization liquid S1 and S2, after 20 DEG C of stirring 2h of room temperature, obtains crystallization mixed liquor, and will
It was moved into reaction kettle with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 6 hours.Products therefrom is washed through deionized water centrifugation
After washing, filter, drying, 8 hours are roasted in 550 DEG C in air atmosphere to get SAPO-34/SAPO-18 composite molecular screen C1,
Wherein, weight percentage shared by SAPO-18 molecular sieves is about 51.2%, and sample XRD spectra by Fig. 1 as shown in Figure 1, can be seen
Going out, composite molecular screen is in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ±
0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc. go out
Existing characteristic peak, and 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, it is SAPO-34 that (25.1 ± 0.1) °, which are waited,
The characteristic peak of molecular sieve, 2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ±
0.1) °, (17.6 ± 0.1) it is ° equal be SAPO-18 molecular sieves characteristic peak, i.e., existed simultaneously in composite molecular screen SAPO-34 phases and
SAPO-18 phases.
Embodiment 2
1) boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 6.84g deionized waters are mixed respectively
It stirs, the Ludox 4.50g that solid content is 40 weight % is added dropwise after 1 hour in strong stirring, and uniformly rear addition to be mixed is a concentration of
Tetraethyl ammonium hydroxide (TEAOH) aqueous solution 55.24g of 20 weight % continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Gained is former
Each component molar ratio of material is in material mixture A：1.5TEAOH:0.6SiO2:Al2O3:P2O5:65H2O.By above-mentioned gel material
Mixture A is fitted into the reaction kettle with polytetrafluoro liner, in the pre- crystallization of 200 DEG C of hydro-thermals 6 hours, obtains pre- crystallization liquid S1；
The boehmite of 8.22g, 10.37g phosphoric acid (85 weight % of concentration) and 39.95g deionized waters are mixed respectively
It stirs, the Ludox 0.75g that solid content is 40 weight %, uniformly rear addition template to be mixed is added dropwise after 1 hour in strong stirring
N,N-diisopropylethylamine (DIEA) 12.92g continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Each group in gained raw mixture B
Point molar ratio of material is：2DIEA:0.1SiO2:Al2O3:0.9P2O5:50H2O.Above-mentioned gel material mixture B loadings are had
In the reaction kettle of polytetrafluoro liner, in the pre- crystallization of 180 DEG C of hydro-thermals 12 hours, pre- crystallization liquid S2 is obtained；
2) in mass ratio 2:1 mixes pre- crystallization liquid S1 and S2, after 20 DEG C of stirring 2h of room temperature, obtains crystallization mixed liquor, and will
It was moved into reaction kettle with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 12 hours.Products therefrom is washed through deionized water centrifugation
After washing, filter, drying, 8 hours are roasted in 550 DEG C in air atmosphere to get SAPO-34/SAPO-18 composite molecular screen C2,
Wherein, weight percentage shared by SAPO-18 molecular sieves is about 42.2%, and sample XRD spectra by Fig. 1 as shown in Figure 1, can be seen
Going out, composite molecular screen is in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ±
0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc. go out
Existing characteristic peak, and 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, it is SAPO-34 that (25.1 ± 0.1) °, which are waited,
The characteristic peak of molecular sieve, 2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ±
0.1) °, (17.6 ± 0.1) it is ° equal be SAPO-18 molecular sieves characteristic peak, i.e., existed simultaneously in composite molecular screen SAPO-34 phases and
SAPO-18 phases.
Embodiment 3
1) respectively that the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 42.93g deionized waters is mixed
Conjunction is stirred, and the Ludox 4.5g that solid content is 40 weight %, uniformly rear addition template to be mixed is added dropwise after 1 hour in strong stirring
Agent triethylamine (TEA) 10.12g continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Each component material mole in gained raw mixture A
Than for：2TEA:0.6SiO2:Al2O3:P2O5:55H2O.Above-mentioned gel material mixture A is packed into anti-with polytetrafluoro liner
It answers in kettle, in the pre- crystallization of 200 DEG C of hydro-thermals 10 hours, obtains pre- crystallization liquid S1；
The boehmite of 8.22g, 10.37g phosphoric acid (85 weight % of concentration) and 48.95g deionized waters are mixed respectively
It stirs, the Ludox 0.75g that solid content is 40 weight %, uniformly rear addition template to be mixed is added dropwise after 1 hour in strong stirring
N,N-diisopropylethylamine (DIEA) 7.75g continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Each component in gained raw mixture B
Molar ratio of material is：1.2DIEA:0.1SiO2:Al2O3:0.95P2O5:60H2O.Above-mentioned gel material mixture B loadings are had
In the reaction kettle of polytetrafluoro liner, in the pre- crystallization of 180 DEG C of hydro-thermals 9 hours, pre- crystallization liquid S2 is obtained；
2) in mass ratio 1:2 mix pre- crystallization liquid S1 and S2, after 20 DEG C of stirring 2h of room temperature, obtain crystallization mixed liquor, and will
It was moved into reaction kettle with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 8 hours.Products therefrom is washed through deionized water centrifugation
After washing, filter, drying, 8 hours are roasted in 550 DEG C in air atmosphere to get SAPO-34/SAPO-18 composite molecular screen C3,
Wherein, weight percentage shared by SAPO-18 molecular sieves is about 67.7%, and sample XRD spectra by Fig. 1 as shown in Figure 1, can be seen
Going out, composite molecular screen is in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ±
0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc. go out
Existing characteristic peak, and 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, it is SAPO-34 that (25.1 ± 0.1) °, which are waited,
The characteristic peak of molecular sieve, 2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ±
0.1) °, (17.6 ± 0.1) it is ° equal be SAPO-18 molecular sieves characteristic peak, i.e., existed simultaneously in composite molecular screen SAPO-34 phases and
SAPO-18 phases.
Embodiment 4
1) respectively that the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 38.88g deionized waters is mixed
Conjunction is stirred, and the Ludox 2.25g that solid content is 40 weight %, uniformly rear addition template to be mixed is added dropwise after 1 hour in strong stirring
Agent triethylamine (TEA) 10.12g and diethylamine (DEA) 3.66g continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Gained raw material mixes
Each component molar ratio of material is in object A：2TEA:DEA:0.3SiO2:Al2O3:P2O5:50H2O.By above-mentioned gel material mixture A
It is fitted into the reaction kettle with polytetrafluoro liner, in the pre- crystallization of 200 DEG C of hydro-thermals 5 hours, obtains pre- crystallization liquid S1；
The boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 2.8g deionized waters are mixed respectively and stirred
It mixes, the Ludox 0.75g that solid content is 40 weight %, uniformly rear addition a concentration of 20 to be mixed is added dropwise after 1 hour in strong stirring
Tetraethyl ammonium hydroxide (TEAOH) aqueous solution 55.23g of weight % continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Gained raw material
Each component molar ratio of material is in mixture B：1.5TEAOH:0.1SiO2:Al2O3:P2O5:58H2O.Above-mentioned gel material is mixed
It closes object B to be fitted into the reaction kettle with polytetrafluoro liner, in the pre- crystallization of 180 DEG C of hydro-thermals 12 hours, obtains pre- crystallization liquid S2；
2) in mass ratio 5:1 mixes pre- crystallization liquid S1 and S2, after 2h is stirred at room temperature, obtains crystallization mixed liquor, and moved
Enter in the reaction kettle with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 6 hours.Products therefrom is through deionized water centrifuge washing, mistake
After filter, drying, 8 hours are roasted to get SAPO-34/SAPO-18 composite molecular screens C4 in 550 DEG C in air atmosphere, wherein
Weight percentage shared by SAPO-18 molecular sieves is about 39.6%, and sample XRD spectra is as shown in Figure 1, as seen from Figure 1, answer
Molecular sieve is closed in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ± 0.1) °,
There is feature in (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc.
Peak, and 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, it is SAPO-34 molecular sieves that (25.1 ± 0.1) °, which are waited,
Characteristic peak, 2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °,
(17.6 ± 0.1) ° equal characteristic peak for SAPO-18 molecular sieves, i.e., exist simultaneously SAPO-34 phases and SAPO- in composite molecular screen
18 phases.
Embodiment 5
1) aluminium isopropoxide of 22.30g, 11.53g phosphoric acid (85 weight % of concentration) and 30.71g deionized waters are mixed respectively
It stirs, the Ludox 3.75g that solid content is 40 weight %, uniformly rear addition template to be mixed is added dropwise after 1 hour in strong stirring
Triethylamine (TEA) 10.12g continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Each component molar ratio of material in gained raw mixture A
For：2TEA:0.5SiO2:Al2O3:P2O5:40H2O.Above-mentioned gel material mixture A is packed into the reaction with polytetrafluoro liner
In kettle, in the pre- crystallization of 200 DEG C of hydro-thermals 5 hours.Obtain pre- crystallization liquid S1；
The aluminium isopropoxide of 22.30g, 11.53g phosphoric acid (85 weight % of concentration) and 35.05g deionized waters are mixed respectively and stirred
It mixes, Ludox 1.13g, the uniformly rear addition template N to be mixed that solid content is 40 weight % is added dropwise after 1 hour in strong stirring,
N- diisopropylethylamine (DIEA) 9.69g continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Each component object in gained raw mixture B
Expect that molar ratio is：1.5DIEA:0.15SiO2:Al2O3:P2O5:45H2O.Above-mentioned gel material mixture B, which is packed into, has poly- four
In the reaction kettle of fluorine liner, in the pre- crystallization of 180 DEG C of hydro-thermals 10 hours.Obtain pre- crystallization liquid S2；
2) in mass ratio 10:1 mixes pre- crystallization liquid S1 and S2, after 2h is stirred at room temperature, obtains crystallization mixed liquor, and moved
Enter in the reaction kettle with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 6 hours.Products therefrom is through deionized water centrifuge washing, mistake
After filter, drying, 8 hours are roasted to get SAPO-34/SAPO-18 composite molecular screens C5 in 550 DEG C in air atmosphere, wherein
Weight percentage shared by SAPO-18 molecular sieves is about 30.4%, and sample XRD spectra is as shown in Figure 1, as seen from Figure 1, answer
Molecular sieve is closed in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ± 0.1) °,
There is feature in (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc.
Peak, and 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, it is SAPO-34 molecular sieves that (25.1 ± 0.1) °, which are waited,
Characteristic peak, 2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °,
(17.6 ± 0.1) ° equal characteristic peak for SAPO-18 molecular sieves, i.e., exist simultaneously SAPO-34 phases and SAPO- in composite molecular screen
18 phases.
Embodiment 6
1) respectively that the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 38.88g deionized waters is mixed
Conjunction is stirred, and the Ludox 2.25g that solid content is 40 weight %, uniformly rear addition template to be mixed is added dropwise after 1 hour in strong stirring
Agent triethylamine (TEA) 10.12g continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Each component material mole in gained raw mixture A
Than for：2TEA:0.3SiO2:Al2O3:P2O5:50H2O.Above-mentioned gel material mixture A is packed into anti-with polytetrafluoro liner
It answers in kettle, in the pre- crystallization of 200 DEG C of hydro-thermals 6 hours.Obtain pre- crystallization liquid S1；
The boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 2.8g deionized waters are mixed respectively and stirred
It mixes, the Ludox 0.75g that solid content is 40 weight %, uniformly rear addition a concentration of 20 to be mixed is added dropwise after 1 hour in strong stirring
Tetraethyl ammonium hydroxide (TEAOH) aqueous solution 55.23g of weight % continues to stir 2h, 20 DEG C of ageing 2h of room temperature.Gained raw material
Each component molar ratio of material is in mixture B：1.5TEAOH:0.1SiO2:Al2O3:P2O5:58H2O.Above-mentioned gel material is mixed
It closes object B to be fitted into the reaction kettle with polytetrafluoro liner, in the pre- crystallization of 180 DEG C of hydro-thermals 9 hours, obtains pre- crystallization liquid S2；
2) in mass ratio 1:1 mixes pre- crystallization liquid S1 and S2, after 20 DEG C of stirring 2h of room temperature, obtains crystallization mixed liquor, and will
It was moved into reaction kettle with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 6 hours.Products therefrom is washed through deionized water centrifugation
After washing, filter, drying, 8 hours are roasted in 550 DEG C in air atmosphere to get SAPO-34/SAPO-18 composite molecular screen C6,
Wherein, weight percentage shared by SAPO-18 molecular sieves is about 55.2%, and sample XRD spectra by Fig. 1 as shown in Figure 1, can be seen
Going out, composite molecular screen is in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ±
0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc. go out
Existing characteristic peak, and 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, it is SAPO-34 that (25.1 ± 0.1) °, which are waited,
The characteristic peak of molecular sieve, 2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ±
0.1) °, (17.6 ± 0.1) it is ° equal be SAPO-18 molecular sieves characteristic peak, i.e., existed simultaneously in composite molecular screen SAPO-34 phases and
SAPO-18 phases.
Comparative example 1
SAPO-34/SAPO-18 composite molecular screens are synthesized according to method disclosed in CN102372291A.
Boehmite 13.15g is dissolved in 29.76g deionized waters, under stirring, phosphoric acid (85 weight % of concentration) is added dropwise
16.60g and 14.88g deionized water mixed liquors, after stirring 1h, add Ludox (solid content be 40 weight %) 7.2g and
14.88g deionized water mixed liquor.Continue after stirring 1h, template n,N-diisopropylethylamine 15.51g and 5.85g is added
DEA, is mixed 2h, and room temperature is aged 2h；
Above-mentioned solution is moved into crystallizing kettle, hydrothermal crystallizing 96h at 180 DEG C.Solid crystallized product is centrifuged through deionized water
After washing and filtering, dry 5h, obtains SAPO-34/SAPO-18 composite molecular screen original powders at 120 DEG C.650 DEG C in air atmosphere
Lower roasting 8h is to get SAPO-34/SAPO-18 composite molecular screens D1, wherein weight percentage shared by SAPO-18 molecular sieves is about
It is 87.9%, sample XRD spectra is as shown in Figure 1, as seen from Figure 1, and composite molecular screen is in 2 θ=(9.5 ± 0.1) °, and (15.9
± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5
± 0.1) °, (16.9 ± 0.1) °, there is characteristic peak in (17.6 ± 0.1) ° etc., and 2 θ=(9.5 ± 0.1) °, (15.9 ±
0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) it is ° equal be SAPO-34 molecular sieves characteristic peak, 2 θ=(9.5 ± 0.1) °,
(10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, it is SAPO-18 points that (17.6 ± 0.1) °, which are waited,
The characteristic peak of son sieve, i.e., exist simultaneously SAPO-34 phases and SAPO-18 phases in composite molecular screen.
Comparative example 2
SAPO-34/SAPO-18 composite molecular screens are synthesized according to crystal seed method disclosed in CN103418431A.
10.36g boehmites and 21.73g deionized waters are mixed, silicon source solution is formed, it will under stirring
11.84g phosphoric acid (a concentration of 85 weight %) and the mixed solution of 12.15g deionized waters are added dropwise, and after stirring 1h, are added
The silicon source solution of 7.35g Ludox and 19.85g deionized waters.After stirring evenly, template triethylamine 16.38g is added, continues
After stirring 2h, SAPO-18 molecular sieve seeds 0.5g is added.2h is stirred, ageing is for 24 hours.
Above-mentioned solution is moved into crystallizing kettle, hydrothermal crystallizing 48h at 200 DEG C.Solid crystallized product is centrifuged through deionized water
After washing and filtering, dry 5h, obtains SAPO-34/SAPO-18 composite molecular screen original powders at 120 DEG C.650 DEG C in air atmosphere
Lower roasting 8h is to get SAPO-34/SAPO-18 composite molecular screens D2, wherein weight percentage shared by SAPO-18 molecular sieves is about
It is 10.3%, sample XRD spectra is as shown in Figure 1, as seen from Figure 1, and composite molecular screen is in 2 θ=(9.5 ± 0.1) °, and (15.9
± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5
± 0.1) °, (16.9 ± 0.1) °, there is characteristic peak in (17.6 ± 0.1) ° etc., and 2 θ=(9.5 ± 0.1) °, (15.9 ±
0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) it is ° equal be SAPO-34 molecular sieves characteristic peak, 2 θ=(9.5 ± 0.1) °,
(10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °, it is SAPO-18 points that (17.6 ± 0.1) °, which are waited,
The characteristic peak of son sieve, i.e., exist simultaneously SAPO-34 phases and SAPO-18 phases in composite molecular screen.
Test case
The composite molecular screen D1-D2 that composite molecular screen C1-C6 prepared by previous embodiment 1-6 is prepared with comparative example 1-2
For the reaction of preparing light olefins from methanol, specific steps and condition are as follows：
Using fixed bed catalyst evaluating apparatus, the sieve sample that embodiment 1-6 and comparative example 1-2 are obtained carries out
Examination experiment, weighs 1.0 grams by above-mentioned sample respectively and is put into reactor, nitrogen activation is led at 500 DEG C 0.5 hour, then
450 DEG C are cooled to, material benzenemethanol solution is mixed into preheating furnace after flow measurement pumps under the carrying of carrier gas-nitrogen,
Gas is vaporized into preheating furnace, subsequently into being reacted in reactor, nitrogen flow rate 200ml/min, methanol weight air speed is
3.0h-1, product is analyzed using offline gas-chromatography after reaction, wherein when occurring alcohol and ether group timesharing in spectrogram, illustrates first
Alcohol conversion has not been 100%, stops experiment at this time.Specific experiment result is referring to table 1.
The SAPO-34/SAPO-18 composite molecular screens prepared using the method for the present invention it can be seen from 1 result of table are averaged the longevity
It orders longer, good low-carbon alkene average selectivity is shown in methanol to olefins reaction.Compared with comparative example molecular sieve, adopt
Have longer catalysis (use) service life, better low-carbon alkene average with the molecular sieve synthesized by (embodiment) method of the invention
Selectivity.Meanwhile ethylene, propylene ratio can be with each molecular sieve different proportion in composite molecular screen in the larger context in product
Regulated and controled.
Table 1
In table 1, C4+Indicate the blending ingredients of C4 substances.
Table 1 the result shows that：Due to the present invention (embodiment 1-6) use SAPO-34/SAPO-18 molecular sieves individually at
The method of core and syntrophism, compared with the method being nucleated jointly used by comparative example 1-2 with syntrophism, SAPO-34/
The development and growth of SAPO-18 composite molecular screens are more ripe and complete, this is also molecular sieve catalytic prepared by the method for the present invention
The basic reason that performance (carbon olefin average selectivity) and service life improve.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (12)
1. a kind of method preparing double micropore SAPO-34/SAPO-18 composite molecular screens, including：
(1) will carry out pre- crystallization for synthesizing the raw mixture A of SAPO-34 makes pre- crystallization obtain the pre- crystallization without solid
Liquid S1；Pre- crystallization is made to obtain the pre- crystallization liquid without solid by pre- crystallization is carried out for synthesizing the raw mixture B of SAPO-18
S2；
(2) crystallization will be carried out after pre- crystallization liquid S1 and pre- crystallization liquid S2 mixing, solid is isolated from crystallization liquid, dries or does not do
It is roasted after dry；
Wherein, pre- crystallization is the process for the hydrothermal synthesis reaction to form SAPO-34 nucleus and SAPO-18 nucleus, and crystallization is to make
The process of SAPO-34 nucleus and SAPO-18 nucleus growths and the hydrothermal synthesis reaction grown up.
2. according to the method described in claim 1, wherein,
In the raw mixture A, the molar ratio of material is aR1:bSiO2:Al2O3:cP2O5:dH2O, wherein R1 indicates template
Agent R1, a are ranging from：0.1-3, b are ranging from：0.1-1, c are ranging from：0.5-1.8, d are ranging from：20-100；
In the raw mixture B, the molar ratio of material is aR2:bSiO2:Al2O3:cP2O5:dH2O, wherein R2 indicates template
Agent R2, a are ranging from：0.5-3, b are ranging from：0.01-0.3, c are ranging from：0.6-1.5, d are ranging from：10-100.
3. according to the method described in claim 1, wherein,
The condition of the pre- crystallization of raw mixture A includes：Temperature is 150-210 DEG C, time 1-12h；
The condition of the pre- crystallization of raw mixture B includes：Temperature is 150-210 DEG C, time 1-12h.
4. according to the method described in any one of claim 1-3, wherein the mixing weight of pre- crystallization liquid S1 and pre- crystallization liquid S2
Amount ratio is (0.01-100):1.
5. according to the method described in claim 4, wherein, the mixed weight ratio of pre- crystallization liquid S1 and pre- crystallization liquid S2 are
(0.5-10):1。
6. according to the method described in any one of claim 1-3, wherein in step (2), the condition of crystallization includes：Temperature
It it is 150-210 DEG C, the time is 1-24 hours.
7. according to the method described in any one of claim 1-3, wherein
The raw mixture A is obtained by being aged after silicon source A, deionized water, phosphorus source A, silicon source A and template R1 mixing, wherein
The condition of ageing includes：Temperature is room temperature, time 1-24h；
The raw mixture B is obtained by being aged after silicon source B, deionized water, phosphorus source B, silicon source B and template R2 mixing, wherein
The condition of ageing includes：Temperature is room temperature, time 1-24h.
8. according to the method described in claim 7, the silicon source A and silicon source B each are selected from ethyl orthosilicate, Ludox and hard charcoal
It is one or more in black；Source of aluminium A and silicon source B each is selected from one kind in boehmite, Aluminum sol and aluminium isopropoxide
Or it is a variety of；Phosphorus source A and phosphorus source B each are selected from phosphoric acid and/or phosphorous acid.
9. according to the method described in claim 2, wherein,
The template R1 is one or more in triethylamine, diethylamine, tetraethyl ammonium hydroxide, n-butylamine and morpholine；
The template R2 is selected from tetraethyl ammonium hydroxide and/or N, N- diisopropylethylamine.
10. double micropore SAPO-34/SAPO-18 composite molecular screens that the method described in any one of claim 1-9 obtains.
11. double micropore SAPO-34/SAPO-18 composite molecular screens according to any one of claims 10 are in organic oxygen-containing compound low-carbon
As the application of catalyst activity component in alkene.
12. application according to claim 11, wherein the organic oxygen-containing compound is methanol and/or dimethyl ether.
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| CN109354035B (en) * | 2018-11-24 | 2023-01-24 | 江西师范大学 | Method for preparing AlPO-18 molecular sieve by using double templates |
| CN109759128B (en) * | 2019-02-22 | 2021-12-28 | 山东齐鲁华信高科有限公司 | Preparation method and application of SCR catalyst active component |
| CN110422856A (en) * | 2019-07-05 | 2019-11-08 | 中节能万润股份有限公司 | Sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its application being catalyzed in SCR |
| CN112456511B (en) * | 2019-09-06 | 2022-12-27 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
| CN113753916B (en) * | 2020-06-01 | 2023-05-02 | 中国石油化工股份有限公司 | SAPO composite molecular sieve, preparation method and application thereof |
| CN112520752B (en) * | 2020-12-24 | 2023-02-28 | 山东齐鲁华信高科有限公司 | Rapid synthesis method of SAPO-34/SAPO-11 composite molecular sieve |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208149A (en) * | 2005-06-27 | 2008-06-25 | 埃克森美孚化学专利公司 | Process for manufacture of silicoaluminophosphate molecular sieves |
| CN102633279A (en) * | 2012-04-17 | 2012-08-15 | 清华大学 | Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof |
| CN103418431A (en) * | 2013-08-28 | 2013-12-04 | 神华集团有限责任公司 | SAPO-34/SAPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound and preparation method thereof |
| CN103833047A (en) * | 2014-03-28 | 2014-06-04 | 神华集团有限责任公司 | SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7622624B2 (en) * | 2004-04-05 | 2009-11-24 | Exxonmobil Chemical Patents Inc. | Crystalline intergrowth material, its synthesis and its use in the conversion of oxygenates to olefins |
| US7090814B2 (en) * | 2004-11-10 | 2006-08-15 | Exxonmobil Chemical Patents Inc. | Method of synthesizing silicoaluminophosphate molecular sieves |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208149A (en) * | 2005-06-27 | 2008-06-25 | 埃克森美孚化学专利公司 | Process for manufacture of silicoaluminophosphate molecular sieves |
| CN102633279A (en) * | 2012-04-17 | 2012-08-15 | 清华大学 | Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof |
| CN103418431A (en) * | 2013-08-28 | 2013-12-04 | 神华集团有限责任公司 | SAPO-34/SAPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound and preparation method thereof |
| CN103833047A (en) * | 2014-03-28 | 2014-06-04 | 神华集团有限责任公司 | SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same |
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