CN106830003A - SSZ-13/SCM-9 composite molecular screens and its synthetic method - Google Patents
SSZ-13/SCM-9 composite molecular screens and its synthetic method Download PDFInfo
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Abstract
The present invention relates to a kind of sial SSZ-13/SCM-9 composite molecular screens and its synthetic method,The skeleton structure for mainly solving molecule sieve porous material in the prior art is single,Strong and weak acid site total amount is less,Catalysis activity technical problem not high,The present invention is by using a kind of sial SSZ-13/SCM-9 composite molecular screens,It is characterized in that a kind of sial SSZ-13/SCM-9 composite molecular screens have two kinds of thing phases of SSZ-13 molecular sieves and SCM-9 molecular sieves,Its XRD diffracting spectrum is 6.56 ± 0.05 in 2 θ,9.48±0.02,13.18±0.1,15.88±0.1,19.83±0.1,22.17±0.1,25.48±0.1,30.57±0.1,37.79±0.05,Occurs the technical scheme of diffraction maximum at 43.59 ± 0.05,Preferably solve above mentioned problem,The composite molecular sieves can be used in the industrial production of Downstream Products of Methanol.
Description
Technical field
The present invention relates to a kind of sial SSZ-13/SCM-9 composite molecular screens and its synthetic method.
Background technology
Porous material is the solid compounds that a class has regular pore structure, according to international pure and applied chemistry federation
(IUPAC) definition, porous material can be divided into following three class by their bore dia：Material of the aperture less than 2nm is micro-
Porous materials (micropore materials)；Material of the aperture between 2 to 50nm is mesoporous material (mesopore materials)；
Material of the aperture more than 50nm is large pore material (macropore materials), and zeolite molecular sieve channel diameter is general in 2nm
Hereinafter, therefore it is classified as poromerics.
Zeolite molecular sieve is a kind of silicate material of crystallization, by silicon-oxy tetrahedron [SiO4]4-With aluminum-oxygen tetrahedron [AlO4]5-It is logical
Cross shared oxygen atom to be formed by connecting, be referred to as TO4Tetrahedron (primary structure unitses), element silicon therein can also be by it
Its element, particularly the part same order elements such as some trivalents or quadrivalent element such as Al, B, Ga, Ge, Ti, due to its knot
Some particularity on structure and chemical property, zeolite molecular sieve all has extensive in catalysis, the field such as absorption and ion exchange
Using.A key factor for determining molecular sieve application performance is its duct or cage cave feature, and these are characterized in by molecule
What the intrinsic crystal structure of sieve was determined, thus obtain the molecular sieve of new crystal structure and have for opening up the application of molecular sieve
There is very important meaning.
Some molecular sieves can be obtained from nature, however, major part catalytic field obtain practical application molecular sieve all
It is to be obtained by artificial synthesized method.The forties in last century, Barrer etc. have synthesized nature in the lab first
In non-existent artificial zeolite, in nearly more than ten year thereafter, Milton, Breck and Sand et al. are existed using hydrothermal technique
Alkali metal or alkaline earth metal hydroxide are added in aluminosilicate gels, A types, X-type, L-type and y-type zeolite has been prepared
And modenite etc.；Last century early sixties, with the introducing of organic base cation, a series of brand new zeolites point
Son sieve is prepared out, such as ZSM-n series (ZSM-5 (US 3702886), ZSM-11 (US 3709979), ZSM-23 (US
4076842), ZSM-35 (US 4016245) etc.) zeolite molecular sieve.
Nineteen eighty-two, scientist Wilson S.T. and Flanigen E.M. of American Association Carbide (UCC companies) etc. make
Successfully synthesized with silicon source, phosphorus source and organic formwork agent and have developed a brand-new molecular sieves --- aluminum phosphate point
Son sieve AlPO4-n, n represent model (US4310440).After 2 years, UCC companies are in AlPO4On the basis of-n, make
The Al atoms and P atoms in AlPO skeletons are substituted with Si atomic components, another serial SAPO has been successfully prepared out
Molecular sieve SAPO-n, n represent model (US4440871, US4499327).
1985, the chemist Zones S.I. of Chevron Corporation (Stardard Oil Company of California) synthesized a kind of new molecular sieve SSZ-13.This zeolite is
A kind of chabasie (CHA), its structure is by AlO4And SiO4Tetrahedron is end to end by oxygen atom, arranges in an orderly manner
The elliposoidal crystal structure with octatomic ring structure is arranged into, pore size only has 0.3nm, is divided according to zeolite cavity size,
SSZ-13 belongs to pore zeolite, and specific surface area reaches as high as 700m2/g.Because specific surface area is larger and with octatomic ring
Design feature, SSZ-13 has good heat endurance, can be used as the carrier of adsorbent or catalyst, such as purification of air
Agent, auto-exhaust catalyst etc..SSZ-13 also has cation exchange and acid adjustability simultaneously, thus to various anti-
Answering process has a good catalytic performance, including hydrocarbon compound catalytic cracking, be hydrocracked and alkene and aromatic hydrocarbons construction
Reaction etc..
Above-mentioned molecular sieve is prepared out using the method for Hydrothermal Synthesiss.It can be said that hydrothermal synthesis method is the most frequently used
The method of synthesis of molecular sieve, typical hydrothermal synthesis method have main steps that first by silicon source, silicon source, structure directing agent,
The uniform mixing of the reaction such as alkali and water, obtains starting sol i.e. crystallization mixture, and the crystallization mixture then is placed in into polytetrafluoro again
Ethene be liner, stainless steel for outer wall reactor in, it is closed after carry out crystallization at certain temperature and self-generated pressure,
Such as the process of earth lithogenesis.
The silicon source of synthesis of molecular sieve typically can use Ludox, silica gel, sodium metasilicate, White Carbon black and organosilicon etc., silicon source is general
Using aluminum sulfate, aluminum nitrate, sodium metaaluminate, alumina sol, organo-aluminium and boehmite etc., alkali can be organic
Alkali, ammoniacal liquor, NaOH, KOH etc..Wherein alkali is a key factor for influenceing Zeolite synthesis, but the alkali of excess can make
Molecular sieve dissolves, and reduces product yield, meanwhile, the introducing of inorganic base will make to prepare one step of acidic molecular sieve increase
Suddenly, i.e., to the exchange process of metal cation, the process causes that process costs increase, and wastewater treatment capacity increases.
Such as document (45-51 of Microporous Materials 11 (1997)), document (Microporous and Mesoporous
The 85-96 of Materials 69 (2004)) and document (143-148 of Microporous and Mesoporous Materials 135 (2010))
All ZSM-5 zeolite molecular sieve is synthesized using Magadiite as silicon source or silicon and aluminum source, has also all been added in reaction system
Hydroxide is used as alkali source.
By way of hydrothermal crystallizing, the sial SSZ-13/SCM-9 for selecting appropriate reactant to obtain novelty is answered the present invention
Close molecular sieve.Up to now, about sial SSZ-13/SCM-9 composite molecular screens and its synthetic method document there is not yet
Report.
The content of the invention
One of technical problems to be solved by the invention be molecule sieve porous material skeleton structure is single, strong and weak acid site total amount
Less, catalysis activity technical problem not high, there is provided a kind of sial SSZ-13/SCM-9 composite molecular screens, the molecular sieve
Pore passage structure complex distribution, strong and weak acid site total amount is more, catalysis activity advantage higher.
The two of the technical problems to be solved by the invention are to be not directed to a kind of above-mentioned sial SSZ-13/SCM-9 in the prior art to answer
Close the problem of Zeolite synthesis method, there is provided a kind of preparation method of new sial SSZ-13/SCM-9 composite molecular screens.
The three of the technical problems to be solved by the invention are to provide a kind of sial SSZ-13/SCM-9 composite molecular screens for preparing
The purposes of Downstream Products of Methanol.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of compound point of SSZ-13/SCM-9
Son sieve, it is characterised in that described SSZ-13/SCM-9 composite molecular screens have SSZ-13 molecular sieves and SCM-9 molecular sieves
Two kinds of thing phases, its XRD diffracting spectrum is 6.56 ± 0.05,9.48 ± 0.02,13.18 ± 0.1,15.88 ± 0.1 in 2 θ,
19.83 ± 0.1,22.17 ± 0.1,25.48 ± 0.1,30.57 ± 0.1,37.79 ± 0.05, occur diffraction maximum at 43.59 ± 0.05.
In above-mentioned technical proposal, it is preferred that its XRD diffracting spectrum is 6.56 ± 0.05,9.48 ± 0.02,12.79 in 2 θ
± 0.1,13.18 ± 0.1,14.13 ± 0.1,15.88 ± 0.1,17.18 ± 0.1,18.08 ± 0.1,19.83 ± 0.1,20.62
± 0.1,22.17 ± 0.1,25.48 ± 0.1,28.25 ± 0.1,29.33 ± 0.05,30.23 ± 0.1,30.57 ± 0.1,31.28 ±
0.1,33.39 ± 0.1,37.79 ± 0.05,38.84 ± 0.1,40.81 ± 0.1,43.59 ± 0.05,47.40 ± 0.05,48.21
±0.1
In above-mentioned technical proposal, with the weight in a kind of sial SSZ-13/SCM-9 composite molecular screens, SSZ-13
The weight percentage of molecular sieve is 40~60%；The weight percentage of SCM-9 is 40~60%.
In above-mentioned technical proposal, it is preferred that the weight percentage of SSZ-13 molecular sieves is 40~60%；The weight of SCM-9
Percentage composition is 40~60%.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of sial SSZ-13/SCM-9 is answered
The synthetic method of molecular sieve is closed, is comprised the steps of：
A, with raw materials used molar ratio it is：SiO2/Al2O3=1~5000, template T/Al2O3=1~500, solvent
S/Al2O3=50~1000, a certain amount of silicon source and solvent are mixed to form solution S, by solution S according to certain weight ratio, point
Solution S is designated as into two parts1And solution S2；
B, by a part of silicon source, additive and prepare SSZ-13 needed for organic formwork agent add S1In, stir 0.5~5 hour,
Precipitation obtains solution S after 1~12 hour1’；
C, by remaining silicon source and synthesis SCM-9 needed for organic formwork agent add S2In solution, stir 0.5~5 hour
Mineralizer is added afterwards, continues to obtain solution S after stirring 0.5~5 hour2’；
D, by solution S1' and solution S2' be respectively placed in 80~120 DEG C at hydrothermal pretreatment 12~48 hours and add additive,
Afterwards by solution S1' and solution S2' uniform mixing, continue closed stirring 1~24 hour at 80~120 DEG C, form uniform
Crystallization mixture；
E, the crystallization mixture of above-mentioned steps d is placed in 150~200 DEG C, crystallization 12 hours~15 days, product through filtering,
80~130 DEG C of dryings after washing, then heat to 400~650 DEG C, constant temperature calcining 1~12 hour.
In above-mentioned technical proposal, it is preferred that it is 5~95% that silicon source used by preparing SSZ-13 accounts for total silicon source mass percent；System
It is 5~95% that silicon source used by standby SCM-9 accounts for total silicon source mass percent.
In above-mentioned technical proposal, it is preferred that silicon source used be selected from aluminate, meta-aluminate, aluminium salt, the hydroxide of aluminium,
At least one in the oxide or the mineral containing aluminium of aluminium；Silicon source used be selected from organosilicon, amorphous silica, Ludox,
At least one in solid oxidation silicon, silica gel, diatomite or waterglass.Preferred technical scheme, needed for preparation SSZ-13
Organic formwork agent be organic amine, selected from 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl hydrogen
It is amine-oxides, TBAB, TBAH, amantadine, triethylamine, n-butylamine, di-n-propylamine, two different
At least one in propylamine, ethylenediamine or ethamine；Preferred technical scheme, the organic formwork agent needed for preparing SCM-9 is
Organic amine, selected from 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, the tetrabutyl
Ammonium bromide, TBAH, amantadine, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine or
At least one in ethamine；Mineralizer is fluoride, selected from least one in hydrofluoric acid, ammonium fluoride, sodium fluoride；Addition
Agent is at least one in alkali metal or alkaline-earth metal halogen compound；Solvent is deionized water.
In above-mentioned technical proposal, it is preferred that raw materials used molar ratio is：SiO2/Al2O3=30~1000, template
T/Al2O3=10~100, solvent S/Al2O3=100~500.
In above-mentioned technical proposal, it is preferred that solution S in step a1And solution S2Weight ratio be 0.1~10:1；Step b
In silicon source used account for total silicon source mass percent for 10~90%；Silicon source used accounts for total silicon source mass percent and is in step c
10~90%.
In above-mentioned technical proposal, it is preferred that silicon source is selected from aluminate, meta-aluminate, aluminium salt, the hydroxide of aluminium, aluminium
At least one in oxide or the mineral containing aluminium；Silicon source is selected from organosilicon, amorphous silica, Ludox, solid oxygen
At least one in SiClx, silica gel, diatomite or waterglass；Additive is in alkali metal or alkaline-earth metal halogen compound
It is at least one.
In above-mentioned technical proposal, it is preferred that the organic formwork agent needed for for preparing SSZ-13 is organic amine, selected from 4 third
Base ammonium bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, TBAB, tetrabutylammonium hydrogen
At least one in amine-oxides, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine or ethamine；Preferred skill
Art scheme, organic formwork agent needed for preparing SCM-9 is organic amine, selected from 4-propyl bromide, TPAOH,
Tetraethylammonium bromide, tetraethyl ammonium hydroxide, TBAB, TBAH, triethylamine, n-butylamine, two
At least one solvent in n-propylamine, diisopropylamine, ethylenediamine or ethamine is deionized water.
In above-mentioned technical proposal, it is preferred that it is 20~80% that silicon source used accounts for total silicon source mass percent in step b；Step
Silicon source used accounts for total silicon source mass percent for 20~80% in c, and preferred technical scheme is that silicon source used is accounted in step b
Total silicon source mass percent is 35~65%, and it is 35~65% that silicon source used accounts for total silicon source mass percent in step c；Step a
Middle solution S1And solution S2Weight ratio be 0.2~5:1, preferred technical scheme, solution S1And solution S2Weight ratio
It is 0.5~3:1.
To solve the three of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of sial SSZ-13/SCM-9 is answered
Molecular sieve is closed as catalyst, the catalytic reaction of hydro carbons is prepared for methyl alcohol.
The composite molecular sieves that the present invention is provided have two kinds of pore passage structure features and acidic character of molecular sieve concurrently, and embody
Carry out good cooperative effect.Change the two-phase proportion in composite molecular screen by optimising and adjustment synthesis condition to obtain with optimal
Pore passage structure and suitable acid composite molecular sieves, the course of reaction of hydrocarbon processed is converted for methyl alcohol, in the evaluation of setting
In condition and range, methanol conversion is 100%, product diene (ethene, propylene) and isomery C4Once through yield highest
Up to 84.9%, while catalyst has good stability, preferable technique effect is achieved.
The present invention is further elaborated below by embodiment.
Specific embodiment
【Embodiment 1】
A kind of synthesis of sial SSZ-13/SCM-9 composite molecular screens
By the aluminum sulfate [Al of 1572.75g2(SO4)3·18H2O, purity >=98wt.%] it is dissolved in 1134.36mL water, mixing system
Into solution S, the solution is divided into two parts respectively 80% and 20% by mass fraction afterwards, is designated as solution S1And solution S2,
2429.26g acidic silicasols (40wt.%) and 129.5g TBAHs (TEAOH, 50wt%) are put into
Middle S1, stir 0.5h and obtain solution S1’；By 607.32g acidic silicasols (40wt.%), 211.36g NaOH (NaOH),
136.06g amantadines (TMAdaOH, purity >=98wt.%) put into S2In solution, added after stirring 1h a certain amount of
Mineralizer HF, continue stir 1h obtain solution S2’；By solution S1' and solution S2' be respectively placed in 80 DEG C at hydro-thermal process 48h,
Afterwards by solution S1' and solution S2' the uniform KCl for being mixed and added into accounting for reaction mass gross weight 3.3%, it is closed at 120 DEG C to stir
Mix 12h；By above-mentioned stirring mixture, then 150 DEG C of crystallization 15d are placed in, product dries 5h for 110 DEG C after filtering, washing,
400 DEG C are then heated to, constant temperature calcining 12h both obtains product, is designated as the quality of MA-1, wherein SSZ-13 and SCM-9
Percentage composition is respectively 78% and 22%, and reactant consumption and mol ratio are as shown in table 1.
【Embodiment 2】
A kind of synthesis of sial SSZ-13/SCM-9 composite molecular screens
By the aluminum sulfate [Al of 122.08g2(SO4)3·18H2O, purity >=98wt.%] it is dissolved in 689.48mL water, it is mixed
Solution S, is divided into two parts respectively 70% and 30% by the solution by mass fraction afterwards, is designated as solution S1And solution S2,
457.21g acidic silicasols (40wt.%) and 182.20g amantadines (TMAdaOH, purity >=98wt.%) are thrown
Enter middle S1, stir 20h and obtain solution S1’；By 195.95g acidic silicasols (40wt.%), 211.36g NaOH (NaOH)
And 206.15g amantadines (TMAdaOH, purity >=98wt.%) input S2In solution, one is added after stirring 5h
Quantitative mineralizer NaF, continues stirring 5h and obtains solution S2’；By solution S1' and solution S2' be respectively placed in 100 DEG C at hydro-thermal
Treatment 10h, afterwards by solution S1' and solution S2' uniformly mix the NaCl for adding and accounting for reaction mass gross weight 2.2%, 110 DEG C
Closed stirring 24h；By above-mentioned stirring mixture, then 200 DEG C of crystallization 10h are placed in, product is done for 80 DEG C after filtering, washing
Dry 8h, then heats to 550 DEG C, and constant temperature calcining 9h both obtains product, is designated as MA-2, wherein SSZ-13 and SCM-9
Weight/mass percentage composition be respectively 68% and 32%, reactant consumption and mol ratio are as shown in table 1.
【Embodiment 3】
A kind of synthesis of sial SSZ-13/SCM-9 composite molecular screens
By the aluminum nitrate [Al (NO of 6801.11g3)3·9H2O] it is dissolved in 1568.32mL water, solution S is mixed and made into, afterwards will
The solution is divided into two parts respectively 61% and 39% by mass fraction, is designated as solution S1And solution S2, 5955.10g is acid
Ludox (40wt.%), 629.05 NaOH (NaOH), 360.6g amantadines (TMAdaOH, purity >=98wt.%)
And S in 1122.34g ethylenediamines (TEA) input1, stir 15h and obtain solution S1’；3970.01g acidic silicasols (40wt.%),
523.21g NaOH (NaOH), 629.05g amantadines (TMAdaOH, purity >=98wt.%) input S2Solution
In, a certain amount of mineralizer HF is added after stirring 0.5h, continue stirring 3h and obtain solution S2’；By solution S1' and solution
S2' be respectively placed in 120 DEG C at hydro-thermal process 0.5h, afterwards by solution S1' and solution S2' uniformly be mixed and added into accounting for reaction mass
The KCl and MgCl of gross weight 2.5%2·2H2O, 120 DEG C of closed stirring 0.5h；By above-mentioned stirring mixture, then it is placed in 160 DEG C
Crystallization 9d, product dries 9h for 80 DEG C after filtering, washing, then heats to 650 DEG C, and constant temperature calcining 9h both obtains product,
The weight/mass percentage composition for being designated as MA-3, wherein SSZ-13 and SCM-9 is respectively 59% and 41%, reactant consumption and
Mol ratio is as shown in table 1.
【Embodiment 4】
A kind of synthesis of sial SSZ-13/SCM-9 composite molecular screens
By the aluminum nitrate [Al (NO of 652.1g3)3·9H2O] it is dissolved in 966.66mL water, solution S is mixed and made into, afterwards should
Solution is divided into two parts respectively 53% and 47% by mass fraction, is designated as solution S1And solution S2, by 828.02g acidity silicon
S in colloidal sol (40wt.%) and 1001.54g TBAHs (TPAOH, 50wt%) input1, stir 12h
Obtain solution S1’；By 734.29g acidic silicasols (40wt.%), 495.27g NaOH (NaOH) and 136.06g
Amantadine (TMAdaOH, purity >=98wt.%) puts into S2In solution, a certain amount of mineralizer is added after stirring 3h
HF, continues stirring 12h and obtains solution S2’；By solution S1' and solution S2' be respectively placed in 110 DEG C at hydro-thermal process 3h, afterwards
By solution S1' and solution S2' the uniform NaCl and CaCl for being mixed and added into accounting for reaction mass gross weight 1.5%2·2H2O, 120 DEG C
Closed stirring 5h；By above-mentioned stirring mixture, then 190 DEG C of crystallization 2d are placed in, product 100 DEG C of dryings after filtering, washing
19h, then heats to 650 DEG C, and constant temperature calcining 10h both obtains product, is designated as MA-4, wherein SSZ-13 and SCM-9
Weight/mass percentage composition is respectively 53% and 47%, and reactant consumption and mol ratio are as shown in table 1.
【Embodiment 5】
A kind of synthesis of sial SSZ-13/SCM-9 composite molecular screens
By the sodium metaaluminate [NaAlO of 3685.21g2] be dissolved in 6925.37mL water, solution S is mixed and made into, it is afterwards that this is molten
Liquid is divided into two parts respectively 39% and 61% by mass fraction, is designated as solution S1And solution S2, by 705.25g white carbons (SiO2,
99wt.%), S during 346.96g NaOH (NaOH) and 1033.25g propane diamine (DPA) put into1, stir 6h
Obtain solution S1’；By 504.4g white carbons (SiO2, 99wt.%), 95.71g NaOH (NaOH), 136.06g Buddha's warrior attendants
Alkanamine (TMAdaOH, purity >=98wt.%) and 224.87g di-n-propylamines (DPA) input S2In solution, stirring
A certain amount of mineralizer NH is added after 1.5h4F, continues stirring 8h and obtains solution S2’；By solution S1' and solution S2' respectively
Hydro-thermal process 15h at being placed in 105 DEG C, afterwards by solution S1' and solution S2' uniformly be mixed and added into accounting for reaction mass gross weight
0.53% KCl and CaCl2·6H2O, 120 DEG C of closed stirring 6h；By above-mentioned stirring mixture, then it is placed in 170 DEG C of crystallization
5d, product dries 6h for 120 DEG C after filtering, washing, then heats to 550 DEG C, and constant temperature calcining 8h both obtains product, is designated as
The weight/mass percentage composition of MA-5, wherein SSZ-13 and SCM-9 is respectively 40% and 60%, reactant consumption and mole
Proportioning is as shown in table 1.
Table 1
【Embodiment 6~15】
It is raw materials used to control reaction sorting different ratio (table 3) as shown in table 2 according to the method for embodiment 5, close respectively
Into a kind of sial SSZ-13/SCM-9 composite molecular screens are gone out, the ratio of SSZ-13 and SCM-9 is shown in Table 4 in material.
Table 2
Table 3
| Embodiment | Reactant ratio is constituted | Sample number into spectrum |
| Embodiment 6 | MA-6 | |
| Embodiment 7 | MA-7 | |
| Embodiment 8 | MA-8 | |
| Embodiment 9 | MA-9 |
| Embodiment 10 | MA-10 | |
| Embodiment 11 | MA-11 | |
| Embodiment 12 | MA-12 | |
| Embodiment 13 | MA-13 | |
| Embodiment 14 | MA-14 | |
| Embodiment 15 | MA-15 |
【Embodiment 16】
A kind of application of sial SSZ-13/SCM-9 composite molecular screens in methyl alcohol converts hydrocarbon reaction processed
The MA-1 molecular sieves of the synthesis of Example 1, carry out ammonium at 80 DEG C with 5wt% ammonium nitrate solutions and exchange 5 hours.Produce
After filtering, washing, drying 6 hours at 100 DEG C, repeat carries out an ammonium and exchanges thing, through filtering, washing, 120 DEG C
After lower drying 3 hours, be calcined 4 hours at 550 DEG C, Hydrogen coexisting molecular sieve be obtained, then compressing tablet, break into pieces, sieve,
The particle for taking 20~40 mesh is standby, is designated as MA1.With methyl alcohol as raw material, with a diameter of 15 millimeters of fixed bed reactors,
In 350 DEG C, mass space velocity 1.5h-1, pressure be 0.1MPa under conditions of check and rate, C2-C4Mass yield reaches 78.4%, takes
Obtained preferable technique effect.
Table 4
【Embodiment 17】
Example it is 2-in-1 into MA-2 molecular sieves, using embodiment 16 method for preparing catalyst be obtained catalyst, note
It is MA2.With methyl alcohol as raw material, with a diameter of 15 millimeters of fixed bed reactors, in 430 DEG C, mass space velocity 5.0h-1、
Pressure is examination, C under conditions of 1.5MPa2-C4Mass yield reaches 82.7%.
【Embodiment 18】
The MA-3 molecular sieves of the synthesis of Example 3, catalyst, note are obtained using the method for preparing catalyst of embodiment 16
It is M3.With methyl alcohol as raw material, with a diameter of 15 millimeters of fixed bed reactors, in 460 DEG C, mass space velocity 3.0h-1, pressure
Power is examination, C under conditions of 5.0MPa2-C4Mass yield reaches 81.5%.
【Embodiment 19】
The MA-4 molecular sieves of the synthesis of Example 4, catalyst, note are obtained using the method for preparing catalyst of embodiment 16
It is M4.With methyl alcohol as raw material, with a diameter of 15 millimeters of fixed bed reactors, in 500 DEG C, mass space velocity 2.5h-1, pressure
Power is examination, C under conditions of 10.0MPa2-C4Mass yield reaches 84.9%.
【Embodiment 20】
The MA-5 molecular sieves of the synthesis of Example 5, catalyst, note are obtained using the method for preparing catalyst of embodiment 16
It is M5.With methyl alcohol as raw material, with a diameter of 15 millimeters of fixed bed reactors, in 530 DEG C, mass space velocity 15.0h-1、
Pressure is examination, C under conditions of 0.5MPa2-C4Mass yield reaches 76.7%.
Claims (10)
1. a kind of SSZ-13/SCM-9 composite molecular screens, it is characterised in that described SSZ-13/SCM-9 compound molecule sifter device
There are two kinds of thing phases of SSZ-13 molecular sieves and SCM-9 molecular sieves, its XRD diffracting spectrum is 6.56 ± 0.05,9.48 in 2 θ
± 0.02,13.18 ± 0.1,15.88 ± 0.1,19.83 ± 0.1,22.17 ± 0.1,25.48 ± 0.1,30.57 ± 0.1,37.79
± 0.05, occur diffraction maximum at 43.59 ± 0.05.
2. SSZ-13/SCM-9 composite molecular screens according to claim 1, it is characterised in that with SSZ-13/SCM-9
The weight of composite molecular screen, the weight percentage of SSZ-13 molecular sieves in described composite molecular sieves
It is 10~90%；The weight percentage of SCM-9 molecular sieves is 10~90%.
3. SSZ-13/SCM-9 composite molecular screens according to claim 2, it is characterised in that with SSZ-13/SCM-9
The weight of composite molecular screen, the weight percentage of SSZ-13 molecular sieves in described composite molecular sieves
It is 40~60%；The weight percentage of SCM-9 molecular sieves is 40~60%.
4. the preparation method of the SSZ-13/SCM-9 composite molecular screens described in claim 1, its synthetic method includes as follows
Several steps：
A, with raw materials used molar ratio it is：SiO2/Al2O3=1~5000, template T/Al2O3=1~500, solvent
S/Al2O3=50~1000, a certain amount of silicon source and solvent are mixed to form solution S, by solution S according to certain weight ratio, point
Solution S is designated as into two parts1And solution S2；
B, by a part of silicon source, additive and prepare SSZ-13 needed for organic formwork agent add S1In, stir 0.5~5 hour,
Precipitation obtains solution S after 1~12 hour1’；
C, by remaining silicon source and synthesis SCM-9 needed for organic formwork agent add S2In solution, stir 0.5~5 hour
Mineralizer is added afterwards, continues to obtain solution S after stirring 0.5~5 hour2’；
D, by solution S1' and solution S2' be respectively placed in 80~120 DEG C at hydrothermal pretreatment 12~48 hours and add additive,
Afterwards by solution S1' and solution S2' uniform mixing, continue closed stirring 1~24 hour at 80~120 DEG C, form uniform
Crystallization mixture；
E, the crystallization mixture of above-mentioned steps d is placed in 150~200 DEG C, crystallization 12 hours~15 days, product through filtering,
80~130 DEG C of dryings after washing, then heat to 400~650 DEG C, constant temperature calcining 1~12 hour.
5. the preparation method of SSZ-13/SCM-9 composite molecular screens according to claim 4, it is characterised in that used
The molar ratio of raw material is：SiO2/Al2O3=30~1000, template T/Al2O3=10~100, solvent S/Al2O3=100~500.
6. the preparation method of SSZ-13/SCM-9 composite molecular screens according to claim 4, it is characterised in that step a
Middle solution C1And solution C2Weight ratio be 0.1~10:1；Silicon source used accounts for total silicon source mass percent and is in step b
10~90%；It is 10~90% that silicon source used accounts for total silicon source mass percent in step c.
7. the preparation method of SSZ-13/SCM-9 composite molecular screens according to claim 4, silicon source be selected from aluminate,
At least one in meta-aluminate, aluminium salt, the hydroxide of aluminium, the oxide of aluminium or the mineral containing aluminium；Silicon source is selected from organic
At least one in silicon, amorphous silica, Ludox, solid oxidation silicon, silica gel, diatomite or waterglass.
8. the preparation method of SSZ-13/SCM-9 composite molecular screens according to claim 4, it is characterised in that be used for
Organic formwork agent needed for preparing SSZ-13 molecular sieves is organic amine, selected from 4-propyl bromide, TPAOH,
Tetraethylammonium bromide, tetraethyl ammonium hydroxide, TBAB, TBAH, amantadine, triethylamine,
At least one in n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine or ethamine；Needed for preparing SCM-9 molecular sieves
Organic formwork agent is organic amine, selected from 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl hydrogen-oxygen
Change ammonium, TBAB, TBAH, amantadine, triethylamine, n-butylamine, di-n-propylamine, diisopropyl
At least one in amine, ethylenediamine or ethamine；Mineralizer is fluoride, selected from hydrofluoric acid, ammonium fluoride, sodium fluoride extremely
Few one kind；Additive is at least one in alkali metal or alkaline-earth metal halogen compound；Solvent is deionized water.
9. the preparation method of SSZ-13/SCM-9 composite molecular screens according to claim 4, it is characterised in that step a
Middle solution C1And solution C2Weight ratio be 0.2~5:1；Silicon source used accounts for total silicon source mass percent and is in step b
20~80%；It is 20~80% that silicon source used accounts for total silicon source mass percent in step c.
10. the purposes of SSZ-13/SCM-9 composite molecular screens described in any one of claims 1 to 3, it is characterised in that：
SSZ-13/SCM-9 composite molecular screens are used in the reaction of methyl alcohol hydro carbons as catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862307A (en) * | 2018-07-26 | 2018-11-23 | 无锡威孚环保催化剂有限公司 | A kind of synthetic method of SSZ-13/MOR eutectic molecular sieve |
| CN109701618A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | AEI composite molecular screen and its synthetic method |
| CN109701619A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | SSZ-13/SSZ-39 composite molecular sieves and its synthetic method |
| CN111530302A (en) * | 2020-04-30 | 2020-08-14 | 上海工程技术大学 | Controllable synthesis method of all-silicon and high-silicon CHA molecular sieve membrane |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514020A (en) * | 2008-02-20 | 2009-08-26 | 中国石油化工股份有限公司 | ZSM-5/beta zeolite/MCM-56 triphase coexisting molecular sieve and method for synthesizing same |
| CN104108727A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | ZSM-11/SAPO-11 dual-structure molecular sieve and synthetic method thereof |
-
2015
- 2015-12-03 CN CN201510881412.5A patent/CN106830003B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514020A (en) * | 2008-02-20 | 2009-08-26 | 中国石油化工股份有限公司 | ZSM-5/beta zeolite/MCM-56 triphase coexisting molecular sieve and method for synthesizing same |
| CN104108727A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | ZSM-11/SAPO-11 dual-structure molecular sieve and synthetic method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701618A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | AEI composite molecular screen and its synthetic method |
| CN109701619A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | SSZ-13/SSZ-39 composite molecular sieves and its synthetic method |
| CN109701618B (en) * | 2017-10-26 | 2021-08-03 | 中国石油化工股份有限公司 | AEI composite molecular sieve and synthesis method thereof |
| CN109701619B (en) * | 2017-10-26 | 2021-10-01 | 中国石油化工股份有限公司 | Molecular sieve with SSZ-13/SSZ-39 composite structure and synthesis method thereof |
| CN108862307A (en) * | 2018-07-26 | 2018-11-23 | 无锡威孚环保催化剂有限公司 | A kind of synthetic method of SSZ-13/MOR eutectic molecular sieve |
| CN108862307B (en) * | 2018-07-26 | 2021-11-19 | 无锡威孚环保催化剂有限公司 | Synthesis method of SSZ-13/MOR eutectic molecular sieve |
| CN112645352A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | SCM-31 molecular sieve and preparation method and application thereof |
| CN112645352B (en) * | 2019-10-12 | 2023-06-06 | 中国石油化工股份有限公司 | SCM-31 molecular sieve and preparation method and application thereof |
| CN112645351B (en) * | 2019-10-12 | 2023-11-28 | 中国石油化工股份有限公司 | SCM-30 molecular sieve and preparation method and application thereof |
| CN111530302A (en) * | 2020-04-30 | 2020-08-14 | 上海工程技术大学 | Controllable synthesis method of all-silicon and high-silicon CHA molecular sieve membrane |
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