CN106564912A - Double-micropore SAPO (silicoaluminophosphate)-34/SAPO-18 composite molecular sieve, and preparation method and application thereof - Google Patents
Double-micropore SAPO (silicoaluminophosphate)-34/SAPO-18 composite molecular sieve, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of molecular sieves, and particularly provides a double-micropore SAPO (silicoaluminophosphate)-34/SAPO-18 composite molecular sieve, and a preparation method thereof. The method comprises the following steps of: (1) carrying out pre-crystallization on a raw material mixture A used for synthesizing SAPO-34 to obtain pre-crystallized liquid S1 which does not contain solids, and carrying out pre-crystallization on a raw material mixture B used for synthesizing SAPO-18 to obtain pre-crystallized liquid S2 which does not contain solids; and (2) mixing the pre-crystallized liquid S1 and the pre-crystallized liquid S2, carrying out crystallization, separating the solids from crystallized liquid, and carrying out roasting after drying is carried out or drying is not carried out. The invention also discloses the application of the double-micropore SAPO-34/SAPO-18 composite molecular sieve in low carbon olefins prepared from organic oxygen-containing compounds. The ratio of the molecular sieve SAPO-34 to the molecular sieve SAPO-18 is adjustable, when the double-micropore SAPO-34/SAPO-18 composite molecular sieve is applied to the industrial production of the low carbon olefins prepared from organic oxygen-containing compounds, an ethylene-propylene ratio in the product is adjustable, and the catalytic activity of the molecular sieve is high.
Description
Technical field
The present invention relates to the preparation method of a kind of pair of micropore SAPO-34/SAPO-18 composite molecular screen, with
And the double micropore SAPO-34/SAPO-18 composite molecular screens obtained by the method for the present invention, and this
Bright double micropore SAPO-34/SAPO-18 composite molecular screens are 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 pore type that three kinds of tetrahedron elements are constituted
Crystal, its crystal structure are showed in reaction for preparing light olefins from methanol similar to Chabazite-type (CHA)
Go out excellent catalytic performance, but easily quickly form carbon distribution during the course of the reaction and cause catalyst rapid
Inactivation.
SAPO-18 molecular sieves are a kind of knots of the AEI with the microcosmic pore passage structure similar with CHA structure
Structure molecular sieve, as its B-acid acid position is less, acid moderate, green coke speed is slower, in methanol-to-olefins
Higher activity stability is shown in reaction.
Research shows that the SAPO-34/SAPO-18 composite molecular screens of double microcellular structures effectively can improve
The acidity of molecular sieve, reduces carbon deposition rate, and then improves its catalytic performance.
CN102372291A discloses a kind of preparation method of SAPO-18/SAPO-34 coexisting molecular sieves.
The method is by using the template tetraethyl ammonium hydroxide that two kinds of things mutually grow is adapted to simultaneously, control is adapted to
Proportioning raw materials in the crystallization liquid of growth, adjust the crystallization temperature that involved thing mutually grows, in hydrothermal condition
Lower synthesis coexisting molecular sieve, crystallization temperature are 150-200 DEG C, and crystallization time is 18-160 hours.
CN103418431A discloses a kind of preparation method of SAPO-34/SAPO-18 composite molecular screens.
The method by using SAPO-18 molecular sieves as crystal seed, with silicon source, phosphorus source, silicon source and template institute
The colloid solution of formation is mixed, and Jing hydrothermal crystallizings obtain composite molecular screen.
The content of the invention
It is an object of the invention on the basis of existing technology, there is provided crystallization time needed for a kind of is short, close
Into efficiency high, the double-micropore composite molecular sieve that two-phase proportion is easily adjusted and catalysis activity is high
The preparation method of SAPO-34/SAPO-18 and the double-micropore composite molecular sieve obtained by the method
SAPO-34/SAPO-18 and its application.
To realize object defined above, according to the first aspect of the invention, the invention provides one kind prepare it is double micro-
The method of hole SAPO-34/SAPO-18 composite molecular screens, including：
(1) pre- crystallization will be carried out so that pre- crystallization is obtained for the raw mixture A for synthesizing SAPO-34
Pre- crystallization liquid S1 without solid；Pre- crystallization will be carried out for the raw mixture B for synthesizing SAPO-18
So that pre- crystallization obtains the pre- crystallization liquid S2 without solid；
(2) crystallization will be carried out after pre- crystallization liquid S1 and pre- crystallization liquid S2 mixing, is separated from crystallization liquid
Go out solid, it is dry or moist after carry out roasting；
Wherein, pre- crystallization is the hydrothermal synthesis reaction to form SAPO-34 nucleus and SAPO-18 nucleus
Process, crystallization are to make SAPO-34 nucleus and SAPO-18 nucleus growths and the hydrothermal synthesis reaction grown up
Process.
According to the second aspect of the invention, the invention provides what is obtained according to the method described in the present invention is double
Micropore SAPO-34/SAPO-18 composite molecular screens.
According to the third aspect of the invention we, the invention provides of the present invention pair of micropore
SAPO-34/SAPO-18 composite molecular screens are in organic oxygen-containing compound producing light olefins as catalyst
The application of active component.
The present invention causes pre- crystalline substance by will carry out pre- crystallization for the raw mixture A for synthesizing SAPO-34
Change obtains the pre- crystallization liquid S1 without solid；To carry out for the raw mixture B for synthesizing SAPO-18
Pre- crystallization causes pre- crystallization to obtain the pre- crystallization liquid S2 without solid, then by pre- crystallization liquid S1 and pre- crystalline substance
Change crystallization after liquid S2 is mixed, it is good to prepare composite effect, pore structure, acidity, catalytic
The double-micropore composite molecular sieve SAPO-34/SAPO-18 of the performances such as energy optimization, uses it for organic oxygen-containing
In the commercial production of compound producing light olefins, in product, ethylene, propylene ratio is adjustable：Can be according to ethylene
The market demand of propylene, carries out the regulation and control of ethylene, propylene in product by the regulation and control of two kinds of molecular sieve ratios.
And the method for the present invention, compared with the methods such as traditional crystal seed method, required crystallization time is short, synthesis
Efficiency high, in composite molecular screen, two-phase proportion is easily adjusted.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with
Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is X-ray diffraction (XRD) figure of embodiment 1-6 and sample synthesized by comparative example 1-2.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
In the present invention, described pair of micropore SAPO-34/SAPO-18 composite molecular screen is referred to described multiple
Simultaneously exist in closing molecular sieve it is biphase, such as in showing X-ray diffraction (XRD) figure, can be simultaneously
There is the characteristic diffraction peak of SAPO-34 and SAPO-18 molecular sieves, wherein, SAPO-34 molecular sieves
Characteristic peak occurs in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1) °
Etc., the characteristic peak of SAPO-18 molecular sieves occurs 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 it was previously stated, the invention provides one kind prepares double micropore SAPO-34/SAPO-18 compound molecules
The method of sieve, the method include：
(1) pre- crystallization will be carried out so that pre- crystallization is obtained for the raw mixture A for synthesizing SAPO-34
Pre- crystallization liquid S1 without solid；Pre- crystallization will be carried out for the raw mixture B for synthesizing SAPO-18
So that pre- crystallization obtains the pre- crystallization liquid S2 without solid；
(2) crystallization will be carried out after pre- crystallization liquid S1 and pre- crystallization liquid S2 mixing, is separated from crystallization liquid
Go out solid, it is dry or moist after carry out roasting.
In the present invention, pre- crystallization is to form SAPO-34 nucleus and the Hydrothermal Synthesiss of SAPO-18 nucleus are anti-
The process answered, crystallization are to make SAPO-34 nucleus and SAPO-18 nucleus growths and the Hydrothermal Synthesiss grown up
The process of reaction.
The method according to the invention, can realize the purpose of the present invention according to preceding solution, described
As long as raw mixture A meets to can be used in synthesizing SAPO-34, for the present invention, preferred institute
State in raw mixture A, the mol ratio of material is aR1:bSiO2:Al2O3:cP2O5:dH2O, wherein,
R1 represents template R1, and the scope of a is：The scope of 0.1-3, b is：The scope of 0.1-1, c is：0.5-1.8,
The scope of d is：20-100.
The method according to the invention, can realize the purpose of the present invention according to preceding solution, described
As long as raw mixture B meets to can be used in synthesizing SAPO-18, for the present invention, preferred institute
State in raw mixture B, the mol ratio of material is aR2:bSiO2:Al2O3:cP2O5:dH2O, wherein,
R2 represents template R2, and the scope of a is：The scope of 0.5-3, b is：The scope of 0.01-0.3, c is：
The scope of 0.6-1.5, d is：10-100.
The method according to the invention, as long as will carry out for the raw mixture A for synthesizing SAPO-34 pre-
Crystallization causes pre- crystallization to obtain the pre- crystallization liquid S1 without solid, the optional model of the condition of pre- crystallization
Enclose wider, for the present invention, the condition of the pre- crystallization of preferred feedstock mixture A includes：Temperature is 150-210
DEG C, used in embodiment for 200 DEG C；The time of more preferably pre- crystallization is 1-12h, preferably 5-10h.
The method according to the invention, as long as will carry out for the raw mixture B for synthesizing SAPO-18 pre-
Crystallization causes pre- crystallization to obtain the pre- crystallization liquid S2 without solid, the optional model of the condition of pre- crystallization
Enclose wider, for the present invention, the condition of the pre- crystallization of preferred feedstock mixture B includes：Temperature is 150-210
DEG C, used in embodiment for 180 DEG C；The time of more preferably pre- crystallization is 1-12h, preferably 9-12h.
The method according to the invention, the mixed proportion of pre- crystallization liquid S1 and pre- crystallization liquid S2 can be according to reality
Border needs to be selected, and by adjusting the ratio of the two, can flexibly adjust double micropores
SAPO-34 and SAPO-18 biphase ratio in SAPO-34/SAPO-18 composite molecular screens, and pass through
Traditional crystal seed method etc. cannot both flexible ratio, in commercial Application extremely inconvenience, this enters
One step shows that the advantage of the present invention is located.
It is of the invention it is a kind of preferred embodiment, the mixing of pre- crystallization liquid S1 and pre- crystallization liquid S2
Part by weight is (0.01-100):1, preferably (0.5-10):1.
The method according to the invention, in step (2), optional wider range of condition of crystallization, for this
Invention, preferably includes：Temperature is 150-210 DEG C, preferably 200 DEG C in embodiment；More preferably
Crystallization time is 1-24 hours, more preferably 6-12 hours.
With the method for the invention it is preferred to the raw mixture A is by silicon source A, deionized water, phosphorus source
It is aged after the mixing of A, silicon source A and template R1 and obtains, wherein, the condition being more preferably aged includes：
Temperature is room temperature, and the time is 1-24h.In the present invention, the mode of mixing is not specially limited, according to this
The routine techniquess mixing in field.
With the method for the invention it is preferred to the raw mixture B is by silicon source B, deionized water, phosphorus source
It is aged after the mixing of B, silicon source B and template R2 and obtains, wherein, the condition being more preferably aged includes：
Temperature is room temperature, and the time is 1-24h.In the present invention, the mode of mixing is not specially limited, according to this
The routine techniquess mixing in field.
The method according to the invention, the present invention to the species of silicon source A and silicon source B without particular/special requirement,
For the present invention, as long as meet, for example
For silicone grease commonly used in the art, Ludox, silicon dioxide, white carbon etc., for the present invention, preferred institute
State silicon source A and silicon source B each is selected from one or more in tetraethyl orthosilicate, Ludox and white carbon.
The method according to the invention, the present invention to the species of source of aluminium A and silicon source B without particular/special requirement,
For the present invention, as long as meet, for example
For boehmite commonly used in the art, Alumina gel, organo-aluminium alcoholate, aluminium oxide etc., for the present invention,
It is preferred that source of aluminium A and silicon source B each are selected from boehmite, Alumina gel and aluminum isopropylate.
Plant or various.
The method according to the invention, the present invention to the species of phosphorus source A and phosphorus source B without particular/special requirement,
For the present invention, as long as meet, for
The present invention, preferred phosphorus source A and phosphorus source B each are selected from phosphoric acid and/or phosphorous acid.
The method according to the invention, the selectable range of the species of template R1 are wider, this area
The conventional template that can be used in preparing SAPO-34 is used equally to the present invention, for the present invention, excellent
Template R1 is selected to be selected from triethylamine, diethylamine, tetraethyl ammonium hydroxide, n-butylamine and morpholine
One or more.
The method according to the invention, the selectable range of the species of template R2 are wider, this area
The conventional template that can be used in preparing SAPO-18 is used equally to the present invention, for the present invention, excellent
Template R2 is selected selected from tetraethyl ammonium hydroxide and/or N, N- diisopropylethylamine.
The present invention causes pre- crystalline substance by will carry out pre- crystallization for the raw mixture A for synthesizing SAPO-34
Change obtains the pre- crystallization liquid S1 without solid；To carry out for the raw mixture B for synthesizing SAPO-18
Pre- crystallization causes pre- crystallization to obtain the pre- crystallization liquid S2 without solid, then by pre- crystallization liquid S1 and pre- crystalline substance
Change crystallization after liquid S2 is mixed, it is good to prepare composite effect, pore structure, acidity, catalytic
The double-micropore composite molecular sieve SAPO-34/SAPO-18 of the performances such as energy optimization.
And the method for the present invention, compared with the methods such as traditional crystal seed method, required crystallization time is short, synthesis
Efficiency high, in composite molecular screen, two-phase proportion is easily adjusted.
The invention provides the double micropore SAPO-34/SAPO-18 obtained according to the method for the present invention are combined
Molecular sieve.
Of the present invention pair of micropore SAPO-34/SAPO-18 compound molecule sieve pore structures, acidity, urge
Change the performances such as performance excellent.
Present invention also offers of the present invention pair of micropore SAPO-34/SAPO-18 composite molecular screen exists
In organic oxygen-containing compound producing light olefins as catalyst activity component application.
, according to the invention it is preferred to the organic oxygen-containing compound is methanol and/or dimethyl ether.
Of the present invention pair of micropore SAPO-34/SAPO-18 composite molecular screen is used for organic oxygen-containing chemical combination
In the commercial production of thing producing light olefins, in product, ethylene, propylene ratio is adjustable：Can be according to ethylene, propylene
The market demand, carry out the regulation and control of ethylene, propylene in product by the regulation and control of two kinds of molecular sieve ratios.
Below by embodiment for whole process is described in detail, but the claim model of the present invention
Enclose and be not restricted by the embodiments.Meanwhile, embodiment has been merely given as the partial condition for realizing this purpose,
But it is not meant to that must being fulfilled for these conditions can just reach this purpose.
In the present invention, XRD spectra is measured by Bruker AXS D8A X-ray diffractometers, work electricity
Pressure 40kV, electric current 40mA, 5 ° -50 ° of sweep limitss.
Embodiment 1
1) respectively by the boehmite (62 weight % of alumina content, same as below) of 8.22g, 11.53g
Phosphoric acid (85 weight % of concentration) and 38.88g deionized waters are mixed, and strong stirring is after 1 hour,
Deca solid content is the Ludox 2.25g of 40 weight %, uniform rear addition template triethylamine to be mixed
(TEA) 10.12g, continues stirring 2h, 20 DEG C of ageing 2h of room temperature；Each group in gained raw mixture A
Point molar ratio of material is：2TEA:0.3SiO2:Al2O3:P2O5:50H2O.By above-mentioned gel material mixture
A loads in the reactor with polytetrafluoro liner, in 200 DEG C of pre- crystallization of hydro-thermal 10 hours, obtains pre- crystalline substance
Change liquid S1；
Respectively by the boehmite (62 weight % of alumina content, same as below) of 8.22g, 11.53g
Phosphoric acid (85 weight % of concentration) and 35.05g deionized waters are mixed, and strong stirring is after 1 hour,
Deca solid content is the Ludox 1.13g of 40 weight %, and uniform rear addition template N to be mixed, N- bis- are different
Propylethylamine (DIEA) 9.69g, continues stirring 2h, 20 DEG C of ageing 2h of room temperature.Gained raw mixture B
Middle each component molar ratio of material is：1.5DIEA:0.15SiO2:Al2O3:P2O5:45H2O.By above-mentioned gel
Raw mixture B loads in the reactor with polytetrafluoro liner, little in the pre- crystallization 10 of 180 DEG C of hydro-thermals
When, obtain pre- crystallization liquid S2；
2) in mass ratio 1:Pre- crystallization liquid S1 and S2 is mixed by 1, after 20 DEG C of stirring 2h of room temperature, obtains brilliant
Change mixed liquor, and move it in the reactor with polytetrafluoro liner, it is little in 200 DEG C of hydrothermal crystallizings 6
When.Products therefrom Jing deionized water centrifuge washing, filtration, be dried after, in 550 DEG C in air atmosphere
Roasting 8 hours, obtains final product SAPO-34/SAPO-18 composite molecular screen C1, wherein, SAPO-18 molecules
Weight percentage shared by sieve is about 51.2%, and sample XRD spectra is as shown in figure 1, can be with by Fig. 1
Find 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) °,
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)
°, characteristic peak of (25.1 ± 0.1) ° grade for SAPO-34 molecular sieves, 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) ° grade are SAPO-18
There is SAPO-34 phases and SAPO-18 phases simultaneously in the characteristic peak of molecular sieve, i.e. composite molecular screen.
Embodiment 2
1) respectively by the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 6.84g
Deionized water is mixed, and after 1 hour, Deca solid content is the Ludox of 40 weight % to strong stirring
4.50g, the uniform rear tetraethyl ammonium hydroxide (TEAOH) for adding concentration to be 20 weight % to be mixed are water-soluble
Liquid 55.24g, continues stirring 2h, 20 DEG C of ageing 2h of room temperature.Each component thing in gained raw mixture A
Expect that mol ratio is：1.5TEAOH:0.6SiO2:Al2O3:P2O5:65H2O.By above-mentioned gel material mixture
A loads in the reactor with polytetrafluoro liner, in 200 DEG C of pre- crystallization of hydro-thermal 6 hours, obtains pre- crystallization
Liquid S1；
Respectively by the boehmite of 8.22g, 10.37g phosphoric acid (85 weight % of concentration) and 39.95g
Deionized water is mixed, and after 1 hour, Deca solid content is the Ludox of 40 weight % to strong stirring
0.75g, uniform rear addition template DIPEA (DIEA) 12.92g to be mixed, continues to stir
Mix 2h, 20 DEG C of ageing 2h of room temperature.In gained raw mixture B, each component molar ratio of material is：
2DIEA:0.1SiO2:Al2O3:0.9P2O5:50H2O.Above-mentioned gel material mixture B is loaded with poly-
In the reactor of tetrafluoro liner, in 180 DEG C of pre- crystallization of hydro-thermal 12 hours, pre- crystallization liquid S2 is obtained；
2) in mass ratio 2:Pre- crystallization liquid S1 and S2 is mixed by 1, after 20 DEG C of stirring 2h of room temperature, obtains brilliant
Change mixed liquor, and move it in the reactor with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 12
Hour.Products therefrom Jing deionized water centrifuge washing, filtration, be dried after, in 550 DEG C in air atmosphere
Roasting 8 hours, obtains final product SAPO-34/SAPO-18 composite molecular screen C2, wherein, SAPO-18 molecules
Weight percentage shared by sieve is about 42.2%, and sample XRD spectra is as shown in figure 1, can be with by Fig. 1
Find 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) °,
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)
°, characteristic peak of (25.1 ± 0.1) ° grade for SAPO-34 molecular sieves, 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) ° grade are SAPO-18
There is SAPO-34 phases and SAPO-18 phases simultaneously in the characteristic peak of molecular sieve, i.e. composite molecular screen.
Embodiment 3
1) respectively by the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 42.93g
Deionized water is mixed, and after 1 hour, Deca solid content is the Ludox of 40 weight % to strong stirring
4.5g, uniform rear addition template triethylamine (TEA) 10.12g to be mixed, continues stirring 2h, room temperature 20
DEG C ageing 2h.In gained raw mixture A, each component molar ratio of material is：2TEA:0.6SiO2:
Al2O3:P2O5:55H2O.Above-mentioned gel material mixture A is loaded into the reactor with polytetrafluoro liner
In, in 200 DEG C of pre- crystallization of hydro-thermal 10 hours, obtain pre- crystallization liquid S1；
Respectively by the boehmite of 8.22g, 10.37g phosphoric acid (85 weight % of concentration) and 48.95g
Deionized water is mixed, and after 1 hour, Deca solid content is the Ludox of 40 weight % to strong stirring
0.75g, uniform rear addition template DIPEA (DIEA) 7.75g to be mixed, continues stirring
2h, 20 DEG C of ageing 2h of room temperature.In gained raw mixture B, each component molar ratio of material is：
1.2DIEA:0.1SiO2:Al2O3:0.95P2O5:60H2O.Above-mentioned gel material mixture B is loaded and is had
In the reactor of polytetrafluoro liner, in 180 DEG C of pre- crystallization of hydro-thermal 9 hours, pre- crystallization liquid S2 is obtained；
2) in mass ratio 1:Pre- crystallization liquid S1 and S2 is mixed by 2, after 20 DEG C of stirring 2h of room temperature, obtains brilliant
Change mixed liquor, and move it in the reactor with polytetrafluoro liner, it is little in 200 DEG C of hydrothermal crystallizings 8
When.Products therefrom Jing deionized water centrifuge washing, filtration, be dried after, in 550 DEG C in air atmosphere
Roasting 8 hours, obtains final product SAPO-34/SAPO-18 composite molecular screen C3, wherein, SAPO-18 molecules
Weight percentage shared by sieve is about 67.7%, and sample XRD spectra is as shown in figure 1, can be with by Fig. 1
Find 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) °,
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)
°, characteristic peak of (25.1 ± 0.1) ° grade for SAPO-34 molecular sieves, 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) ° grade are SAPO-18
There is SAPO-34 phases and SAPO-18 phases simultaneously in the characteristic peak of molecular sieve, i.e. composite molecular screen.
Embodiment 4
1) respectively by the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 38.88g
Deionized water is mixed, and after 1 hour, Deca solid content is the Ludox of 40 weight % to strong stirring
2.25g, uniform rear addition template triethylamine (TEA) 10.12g and diethylamine (DEA) 3.66g to be mixed,
Continue stirring 2h, 20 DEG C of ageing 2h of room temperature.In gained raw mixture A, each component molar ratio of material is：
2TEA:DEA:0.3SiO2:Al2O3:P2O5:50H2O.Above-mentioned gel material mixture A is loaded with poly-
In the reactor of tetrafluoro liner, in 200 DEG C of pre- crystallization of hydro-thermal 5 hours, pre- crystallization liquid S1 is obtained；
Respectively the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 2.8g are gone
Ionized water is mixed, and after 1 hour, Deca solid content is the Ludox 0.75g of 40 weight % to strong stirring,
Uniform rear addition concentration to be mixed is tetraethyl ammonium hydroxide (TEAOH) aqueous solution of 20 weight %
55.23g, continues stirring 2h, 20 DEG C of ageing 2h of room temperature.Each component material in gained raw mixture B
Mol ratio is：1.5TEAOH:0.1SiO2:Al2O3:P2O5:58H2O.By above-mentioned gel material mixture B
Load in the reactor with polytetrafluoro liner, in 180 DEG C of pre- crystallization of hydro-thermal 12 hours, obtain pre- crystallization
Liquid S2；
2) in mass ratio 5:Pre- crystallization liquid S1 and S2 is mixed by 1, after 2h is stirred at room temperature, is obtained crystallization and is mixed
Liquid is closed, and is moved it in the reactor with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 6 hours.
Products therefrom Jing deionized water centrifuge washing, filtration, be dried after, in 550 DEG C of roastings in air atmosphere
8 hours, SAPO-34/SAPO-18 composite molecular screen C4 are obtained final product, wherein, SAPO-18 molecular sieves institute
Account for weight percentage and be about 39.6%, sample XRD spectra as shown in figure 1, as seen from Figure 1,
Composite molecular screen 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. there is characteristic peak, and 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1)
The characteristic peak of ° grade for SAPO-34 molecular sieves, 2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1)
°, (15.5 ± 0.1) °, (16.9 ± 0.1) °, characteristic peak of (17.6 ± 0.1) ° grade for SAPO-18 molecular sieves,
There is SAPO-34 phases and SAPO-18 phases simultaneously i.e. in composite molecular screen.
Embodiment 5
1) respectively by the aluminum isopropylate. of 22.30g, 11.53g phosphoric acid (85 weight % of concentration) and 30.71g
Deionized water is mixed, and after 1 hour, Deca solid content is the Ludox of 40 weight % to strong stirring
3.75g, uniform rear addition template triethylamine (TEA) 10.12g to be mixed, continues stirring 2h, room temperature 20
DEG C ageing 2h.In gained raw mixture A, each component molar ratio of material is：
2TEA:0.5SiO2:Al2O3:P2O5:40H2O.Above-mentioned gel material mixture A is loaded with polytetrafluoro
In the reactor of liner, in 200 DEG C of pre- crystallization of hydro-thermal 5 hours.Obtain pre- crystallization liquid S1；
Respectively the aluminum isopropylate. of 22.30g, 11.53g phosphoric acid (85 weight % of concentration) and 35.05g are gone
Ionized water is mixed, and after 1 hour, Deca solid content is the Ludox 1.13g of 40 weight % to strong stirring,
Uniform rear addition template DIPEA (DIEA) 9.69g to be mixed, continues stirring 2h, room
20 DEG C of ageing 2h of temperature.In gained raw mixture B, each component molar ratio of material is：
1.5DIEA:0.15SiO2:Al2O3:P2O5:45H2O.Above-mentioned gel material mixture B is loaded with poly-
In the reactor of tetrafluoro liner, in 180 DEG C of pre- crystallization of hydro-thermal 10 hours.Obtain pre- crystallization liquid S2；
2) in mass ratio 10:Pre- crystallization liquid S1 and S2 is mixed by 1, after 2h is stirred at room temperature, obtains crystallization
Mixed liquor, and moving it in the reactor with polytetrafluoro liner, in 200 DEG C of hydrothermal crystallizings 6 hours.
Products therefrom Jing deionized water centrifuge washing, filtration, be dried after, in 550 DEG C of roastings in air atmosphere
8 hours, SAPO-34/SAPO-18 composite molecular screen C5 are obtained final product, wherein, SAPO-18 molecular sieves institute
Account for weight percentage and be about 30.4%, sample XRD spectra as shown in figure 1, as seen from Figure 1,
Composite molecular screen 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. there is characteristic peak, and 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) °, (20.5 ± 0.1) °, (25.1 ± 0.1)
The characteristic peak of ° grade for SAPO-34 molecular sieves, 2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1)
°, (15.5 ± 0.1) °, (16.9 ± 0.1) °, characteristic peak of (17.6 ± 0.1) ° grade for SAPO-18 molecular sieves,
There is SAPO-34 phases and SAPO-18 phases simultaneously i.e. in composite molecular screen.
Embodiment 6
1) respectively by the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 38.88g
Deionized water is mixed, and after 1 hour, Deca solid content is the Ludox of 40 weight % to strong stirring
2.25g, uniform rear addition template triethylamine (TEA) 10.12g to be mixed, continues stirring 2h, room temperature 20
DEG C ageing 2h.In gained raw mixture A, each component molar ratio of material is：
2TEA:0.3SiO2:Al2O3:P2O5:50H2O.Above-mentioned gel material mixture A is loaded with polytetrafluoro
In the reactor of liner, in 200 DEG C of pre- crystallization of hydro-thermal 6 hours.Obtain pre- crystallization liquid S1；
Respectively the boehmite of 8.22g, 11.53g phosphoric acid (85 weight % of concentration) and 2.8g are gone
Ionized water is mixed, and after 1 hour, Deca solid content is the Ludox 0.75g of 40 weight % to strong stirring,
Uniform rear addition concentration to be mixed is tetraethyl ammonium hydroxide (TEAOH) aqueous solution of 20 weight %
55.23g, continues stirring 2h, 20 DEG C of ageing 2h of room temperature.Each component material in gained raw mixture B
Mol ratio is：1.5TEAOH:0.1SiO2:Al2O3:P2O5:58H2O.By above-mentioned gel material mixture B
Load in the reactor with polytetrafluoro liner, in 180 DEG C of pre- crystallization of hydro-thermal 9 hours, obtain pre- crystallization liquid
S2；
2) in mass ratio 1:Pre- crystallization liquid S1 and S2 is mixed by 1, after 20 DEG C of stirring 2h of room temperature, obtains brilliant
Change mixed liquor, and move it in the reactor with polytetrafluoro liner, it is little in 200 DEG C of hydrothermal crystallizings 6
When.Products therefrom Jing deionized water centrifuge washing, filtration, be dried after, in 550 DEG C in air atmosphere
Roasting 8 hours, obtains final product SAPO-34/SAPO-18 composite molecular screen C6, wherein, SAPO-18 molecules
Weight percentage shared by sieve is about 55.2%, and sample XRD spectra is as shown in figure 1, can be with by Fig. 1
Find 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) °,
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)
°, characteristic peak of (25.1 ± 0.1) ° grade for SAPO-34 molecular sieves, 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) ° grade are SAPO-18
There is SAPO-34 phases and SAPO-18 phases simultaneously in the characteristic peak of molecular sieve, i.e. composite molecular screen.
Comparative example 1
According to method synthesis SAPO-34/SAPO-18 composite molecular screens disclosed in CN102372291A.
Boehmite 13.15g is dissolved in into 29.76g deionized waters, under stirring, Deca phosphoric acid is (dense
Spend 85 weight %) 16.60g and 14.88g deionized water mixed liquors, after stirring 1h, add Ludox
(solid content is 40 weight %) 7.2g and 14.88g deionized water mixed liquors.After continuing stirring 1h, plus
Enter template DIPEA 15.51g and 5.85g DEA, mix 2h, room temperature ageing
2h；
Above-mentioned solution is moved in crystallizing kettle, hydrothermal crystallizing 96h at 180 DEG C.Solid crystallized product Jing go from
After sub- water centrifuge washing and filtration, 5h is dried at 120 DEG C, obtains SAPO-34/SAPO-18 compound molecules
The former powder of sieve.In air atmosphere, roasting 8h at 650 DEG C, obtains final product SAPO-34/SAPO-18 compound molecules
Sieve D1, wherein, weight percentage shared by SAPO-18 molecular sieves is about 87.9%, sample XRD spectrums
As shown in figure 1, as seen from Figure 1, composite molecular screen is in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) for figure
°, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °,
There is characteristic peak in (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc., and 2 θ=(9.5 ± 0.1)
°, (15.9 ± 0.1) °, (20.5 ± 0.1) °, characteristic peak of (25.1 ± 0.1) ° grade for SAPO-34 molecular sieves,
2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °,
Characteristic peak of (17.6 ± 0.1) ° grade for SAPO-18 molecular sieves, i.e., be present in composite molecular screen simultaneously
SAPO-34 phases and SAPO-18 phases.
Comparative example 2
According to crystal seed method synthesis SAPO-34/SAPO-18 composite molecular screens disclosed in CN103418431A.
10.36g boehmites and 21.73g deionized waters are mixed, silicon source solution is formed, is stirred
Mix the lower mixed solution by 11.84g phosphoric acid (concentration is 85 weight %) and 12.15g deionized waters dropwise
Add, after stirring 1h, add the silicon source solution of 7.35g Ludox and 19.85g deionized waters.Stirring
After uniform, template triethylamine 16.38g is added, after continuing stirring 2h, add SAPO-18 molecular sieves
Crystal seed 0.5g.Stirring 2h, is aged 24h.
Above-mentioned solution is moved in crystallizing kettle, hydrothermal crystallizing 48h at 200 DEG C.Solid crystallized product Jing go from
After sub- water centrifuge washing and filtration, 5h is dried at 120 DEG C, obtains SAPO-34/SAPO-18 compound molecules
The former powder of sieve.In air atmosphere, roasting 8h at 650 DEG C, obtains final product SAPO-34/SAPO-18 compound molecules
Sieve D2, wherein, weight percentage shared by SAPO-18 molecular sieves is about 10.3%, sample XRD spectrums
As shown in figure 1, as seen from Figure 1, composite molecular screen is in 2 θ=(9.5 ± 0.1) °, (15.9 ± 0.1) for figure
°, (20.5 ± 0.1) °, (25.1 ± 0.1) °, (9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °,
There is characteristic peak in (15.5 ± 0.1) °, (16.9 ± 0.1) °, (17.6 ± 0.1) ° etc., and 2 θ=(9.5 ± 0.1)
°, (15.9 ± 0.1) °, (20.5 ± 0.1) °, characteristic peak of (25.1 ± 0.1) ° grade for SAPO-34 molecular sieves,
2 θ=(9.5 ± 0.1) °, (10.4 ± 0.1) °, (10.9 ± 0.1) °, (15.5 ± 0.1) °, (16.9 ± 0.1) °,
Characteristic peak of (17.6 ± 0.1) ° grade for SAPO-18 molecular sieves, i.e., be present in composite molecular screen simultaneously
SAPO-34 phases and SAPO-18 phases.
Test case
Composite molecular screen C1-C6 prepared by previous embodiment 1-6 is divided with the compound of comparative example 1-2 preparation
Son sieve D1-D2 is used for the reaction of preparing light olefins from methanol, and concrete steps and condition are as follows：
Using fixed bed catalyst evaluating apparatus, the molecule that embodiment 1-6 and comparative example 1-2 are obtained
Sieve sample carries out examination experiment, above-mentioned sample is weighed 1.0 grams respectively and is put in reactor, at 500 DEG C
Logical nitrogen activation 0.5 hour, is then cooled to 450 DEG C down, and material benzenemethanol solution is through flow measurement pump
Preheating furnace is mixed under the carrying of carrier gas-nitrogen afterwards, gas, Ran Houjin are vaporized in preheating furnace
Enter in reactor and reacted, nitrogen flow rate 200ml/min, methanol weight air speed are 3.0h-1, after reaction
Product is analyzed using offline gas chromatogram, wherein, when occurring alcohol and ether component in spectrogram, explanation
Methanol conversion has not been 100%, now stops test.Specific experiment result is referring to table 1.
Can be seen that the SAPO-34/SAPO-18 prepared using the inventive method to be combined by 1 result of table
Molecular sieve average life is longer, shows good low-carbon alkene and averagely select in methanol to olefins reaction
Property.Compared with comparative example molecular sieve, had using the molecular sieve synthesized by (embodiment) method of the invention
Longer catalysis (use) life-span, more preferable low-carbon alkene average selectivity.Meanwhile, ethylene in product
Propylene ratio can be regulated and controled in the larger context with each molecular sieve different proportion in composite molecular screen.
Table 1
In table 1, C4+Represent the blending ingredients of C4 materials.
The result of table 1 shows：As (embodiment 1-6) of the invention employs SAPO-34/SAPO-18
The method of the independent nucleation of molecular sieve and syntrophism, the common nucleation adopted compared with comparative example 1-2 and altogether
With the method for growth, the development and growth of SAPO-34/SAPO-18 composite molecular screens is more ripe and complete
Whole, this is also molecular sieve catalytic performance (carbon olefin average selectivity) prepared by the inventive method and uses
The basic reason that life-span improves.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (11)
1. it is a kind of to prepare pair method of micropore SAPO-34/SAPO-18 composite molecular screens, including：
(1) pre- crystallization will be carried out so that pre- crystallization is obtained for the raw mixture A for synthesizing SAPO-34
Pre- crystallization liquid S1 without solid；Pre- crystallization will be carried out for the raw mixture B for synthesizing SAPO-18
So that pre- crystallization obtains the pre- crystallization liquid S2 without solid；
(2) crystallization will be carried out after pre- crystallization liquid S1 and pre- crystallization liquid S2 mixing, is separated from crystallization liquid
Go out solid, it is dry or moist after carry out roasting；
Wherein, pre- crystallization is the hydrothermal synthesis reaction to form SAPO-34 nucleus and SAPO-18 nucleus
Process, crystallization are to make SAPO-34 nucleus and SAPO-18 nucleus growths and the hydrothermal synthesis reaction grown up
Process.
2. method according to claim 1, wherein,
In the raw mixture A, the mol ratio of material is aR1:bSiO2:Al2O3:cP2O5:dH2O,
Wherein, R1 represents template R1, and the scope of a is：The scope of 0.1-3, b is：The scope of 0.1-1, c
For：The scope of 0.5-1.8, d is：20-100；
In the raw mixture B, the mol ratio of material is aR2:bSiO2:Al2O3:cP2O5:dH2O,
Wherein, R2 represents template R2, and the scope of a is：The scope of 0.5-3, b is：0.01-0.3, c's
Scope is：The scope of 0.6-1.5, d is：10-100.
3. method according to claim 1, wherein,
The condition of the pre- crystallization of raw mixture A includes：Temperature is 150-210 DEG C, and the time is 1-12h；
The condition of the pre- crystallization of raw mixture B includes：Temperature is 150-210 DEG C, and the time is 1-12h.
4. the method according to any one in claim 1-3, wherein, pre- crystallization liquid S1 with it is pre-
The mixed weight ratio of crystallization liquid S2 is (0.01-100):1, preferably (0.5-10):1.
5. the method according to any one in claim 1-3, wherein, it is in step (2), brilliant
The condition of change includes：Temperature is 150-210 DEG C, and the time is 1-24 hours.
6. the method according to any one in claim 1-3, wherein,
The raw mixture A is by silicon source A, deionized water, phosphorus source A, silicon source A and template R1
Ageing after mixing is obtained, wherein, the condition of ageing includes：Temperature is room temperature, and the time is 1-24h；
The raw mixture B is by silicon source B, deionized water, phosphorus source B, silicon source B and template R2
Ageing after mixing is obtained, wherein, the condition of ageing includes：Temperature is room temperature, and the time is 1-24h.
7. method according to claim 6, silicon source A and silicon source B each are selected from positive silicic acid
One or more in ethyl ester, Ludox and white carbon；Source of aluminium A and silicon source B each are selected from intending
One or more in boehmite, Alumina gel and aluminum isopropylate.；Phosphorus source A and phosphorus source B are each
Selected from phosphoric acid and/or phosphorous acid.
8. the method according to claim 2 or 6, wherein,
Template R1 is selected from triethylamine, diethylamine, tetraethyl ammonium hydroxide, n-butylamine and morpholine
In one or more；
Template R2 is selected from tetraethyl ammonium hydroxide and/or N, N- diisopropylethylamine.
9. double micropore SAPO-34/SAPO-18 that the method in claim 1-8 described in any one is obtained
Composite molecular screen.
10. the double micropore SAPO-34/SAPO-18 composite molecular screens described in claim 9 contain organic
In oxygen compound producing light olefins as catalyst activity component application.
11. applications according to claim 10, wherein, the organic oxygen-containing compound is methanol
And/or dimethyl ether.
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Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy research institute Address before: 100011 Shenhua building, 22 West Binhe Road, Dongcheng District, Beijing Patentee before: SHENHUA GROUP Corp.,Ltd. Patentee before: Beijing low carbon clean energy research institute |
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