CN106946266B - A kind of SAPO-34/ZSM-12 composite molecular screens and its synthetic method - Google Patents
A kind of SAPO-34/ZSM-12 composite molecular screens and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of SAPO-34/ZSM-12 composite molecular screens and its synthetic method, it is first to prepare aluminium oxide that the composite molecular screen has ZSM-12 molecular sieves crystalline phase and SAPO-34 molecular sieve crystalline phases, synthetic method simultaneously；Then inorganic base, silicon source, silicon source, template and water are mixed, stirs into silica-alumina gel and crystallization certain time；It is subsequently added into the second template, suitable water and aluminium oxide to stir evenly, then evaporates quantitative water；Then ZSM-12 molecular sieves are obtained after hydrothermal crystallizing；Then it is mixed with by phosphorus source, silicon source, silicon source, water and template, SAPO-34/ZSM-12 composite molecular screens is obtained after last hydrothermal crystallizing.The SAPO-34/ZSM-12 composite molecular screens crystallinity of the method for the present invention synthesis is high, not only effectively prevents the generation of stray crystal but also operation is simple.
Description
Technical field
The present invention relates to a kind of SAPO-34/ZSM-12 composite molecular screens and its synthetic method, specifically a kind of low silicon
The synthetic method of aluminium ratio SAPO-34/ZSM-12 composite molecular screens belongs to molecular sieve catalytic material synthesis field.
Background technology
Composite molecular screen is a kind of complex type molecular sieve possessing special construction, is formed by two or more molecular sieves
Cocrystallization, or the composite crystal with two or more molecular sieve structure features.Due to the particularity of compound molecule sieve structure, institute
So that this molecular sieve is provided with the more acidity of reasonable layout and good hydrothermal stability, its component office of itself is overcome
It is sex-limited, the demand of commercial Application is better met, is had broad application prospects.
It is more about the technology of composite molecular screen at present, as CN1583562A discloses a kind of double-micropore zeolites molecular sieve
And preparation method.This method is divided into two big steps, is to synthesize Y type molecular sieve first；Followed by by Y type molecular sieve and tetraethyl
Ammonium bromide, ammonium hydroxide, Ludox mix according to a certain percentage, finally synthesize the composite molecular screen of the bis- microcellular structures of Y/ β.
CN1944254A is the modified patent of CN1583562A, and the main body step of two patented methods is almost the same, area
It is not to be mixed according to a certain percentage with ready-made high-Si Y-type molecular sieve with tetraethylammonium bromide, ammonium hydroxide, Ludox, it is final to synthesize
Go out the composite molecular screen of the bis- microcellular structures of Y/ β.
CN101514009A discloses a kind of mordenite/beta zeolite/Y zeolite coexisting materials and its synthetic method.This method
It is to mix silicon source, silicon source, alkali source, template, water, y-type zeolite crystal seed with dispensing sequence according to a certain percentage, hydrothermal crystallizing goes out
Composite zeolite containing tri- kinds of modenite, β, Y components.
CN101279747A discloses a kind of ZSM-5/ modenites/Y zeolite coexistings molecular sieve and its synthetic method, the party
Method is to mix silicon source, silicon source, alkali source, template, water, y-type zeolite presoma crystal seed with dispensing sequence according to a certain percentage, water
Thermal crystallisation goes out the composite zeolite containing tri- kinds of modenite, ZSM-5, Y components.
CN101514008A discloses a kind of modenite/Y zeolite coexistings molecular sieve and its synthetic method.This method be by
Silicon source, silicon source, alkali source, template and water are mixed in modenite building-up process, and the crystal seed of the body of zeolite precursor containing Y is added,
The nucleation and growth course for controlling molecular sieve have prepared a kind of modenite/Y zeolite coexisting molecular sieves.
CN200410012333.2 discloses a kind of double micro porous molecular sieves and preparation method thereof, is to use orderly synthetic method,
It is raw material first with sodium metasilicate, Ludox, sodium metaaluminate, distilled water, sodium hydroxide, the concentrated sulfuric acid, as at the beginning of certain material proportion
Step synthesizes Y type molecular sieve；It is mixed with the tetraethyl bromination amine aqueous solution dissolved with ammonium hydroxide afterwards, finally adds a certain amount of silicon
Colloidal sol, which is sufficiently stirred, is allowed to uniform, crystallization 4~7 days at 130~140 DEG C, and washing and drying roasting removes template, finally obtains
Composite molecular screen with the bis- microcellular structures of Y/ β.
Invention content
There is also many defects and deficiencies for the synthetic technology of composite molecular screen at present, thus cause the materialization of composite molecular screen
There are certain deficiencies for property.Since synthetic system is more complicated than independent molecular sieve, so as component part in composite molecular screen
The synthesis of component molecular sieve is relatively difficult, especially the extremely difficult control of the physico-chemical properties such as silica alumina ratio of component molecular sieve, is not easy to meet
It is catalyzed the demand of reaction, limits its application in Industrial Catalysis.In view of the deficiencies of the prior art, the present invention provides a kind of
SAPO-34/ZSM-12 composite molecular screens and its synthetic method, the core of the SAPO-34/ZSM-12 composite molecular screens of this method synthesis
Phase ZSM-12 molecular sieves have the feature of low silica-alumina ratio, and whole preparation process is simple and practicable, are suitble to industrialized production.
The present invention provides a kind of SAPO-34/ZSM-12 composite molecular screens, and the composite molecular screen has ZSM-12 points simultaneously
Son sieves crystalline phase and SAPO-34 molecular sieve crystalline phases, the weight of ZSM-12 molecular sieves and SAPO-34 molecular sieves in the composite molecular screen
Amount is than being 1：0.2~2, the oxide silicon al mole ratio of the ZSM-12 molecular sieves is 9~22, preferably 10~20；Compound point
260~800 m of specific surface area of son sieve2/g；0.2~0.7 mmol/g of total acid content of composite molecular screen.
The present invention also provides a kind of synthetic method of SAPO-34/ZSM-12 composite molecular screens recited above, including it is following
Step：
（1）Aluminum nitrate is roasted into 1~5h at 450~700 DEG C, obtains aluminium oxide；
（2）By inorganic base, silicon source, silicon source, water and template (MTEA) according to 1~8Na of molar ratio2O:25~55SiO2:
A12O3:600~2000H2O:The ratio of 2~25MTEA mixes, and obtains silica-alumina gel after stirring evenly, is then charged into reactor
2~20h of crystallization at 140~220 DEG C；
（3）By step（1）Obtained aluminium oxide and step（2）Obtain reactant mixing, and be added the second template and
Water evaporates a certain amount of water at 80~150 DEG C, is then charged into reactor after stirring evenly, brilliant at 140~220 DEG C
Change 24~130h, separating, washing and is dried to obtain ZSM-12 molecular sieves successively；
（4）By phosphorus source, silicon source, silicon source, water and template（M）According to 0.2~1.8P of mol ratio：0.15~1.8SiO2：
A12O3：15~120H2O：The ratio of 0.4~1.7M is uniformly mixed, and step is then added（3）Obtained ZSM-12 molecular sieves, in
15~100h of crystallization at 150~240 DEG C, last separating, washing, drying and roasting obtain compound point of SAPO-34/ ZSM-12
Son sieve.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（1）Described in calcination temperature it is excellent
500~600 DEG C are selected as, roasting time is preferably 1.5~4h.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（2）Described in inorganic base can be with
It is one or more in NaOH, KOH, LiOH；Silicon source can be one kind in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate or
It is a variety of；Silicon source can be one or more in White Carbon black, silica gel, Ludox or waterglass；Template is methyl triethyl group chlorine
Change ammonium（MTEA）.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（2）Described in inorganic base, silicon
Source, silicon source, the mol ratio of water and template (MTEA) are 1.5~7Na2O:30~50SiO2:A12O3:800~1800H2O:4
~20 MTEA.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（2）Described in crystallization condition it is preferred
For 3~16h of crystallization at 170~200 DEG C
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（3）Described in aluminium oxide and step
Suddenly（2）Described in silicon source molar ratio be 15~1SiO2:A12O3, preferably 10~2SiO2:A12O3。
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（3）Described in the second template be
Tetraethylammonium bromide, etamon chloride, second template and step（2）In template molar ratio be 0.5~2,
Preferably 0.8~1.5.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（3）Described in addition water
Volume and step（2）Described in water volume ratio be 0.5~1.5, preferably 0.8~1.2.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（3）Described in need to evaporate it is fixed
The water of amount, after evaporating a certain amount of water, inorganic base, silicon source, silicon source, the molar ratio of water and template are 1~8Na2O:25~
55SiO2:A12O3:50~120H2O:2~25 MTEA, preferably 1.5~7Na2O:30~50SiO2:A12O3:60~100H2O:
4~20 MTEA.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（3）Described in mixing time be
10~60min, preferably 20~50min；Evaporating temperature is 80~150 DEG C, preferably 90~140 DEG C；Crystallization preferably 150~
30~110h of crystallization at 210 DEG C.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（3）Described in separation and washing
Be routine operation well known to those skilled in the art, if detached the method that can take filtering, washing generally refer to spend from
Sub- water washing.Generally include separating for several times and washing operation, generally 1~6 time.Drying condition is usually in 100~140 DEG C of items
Dry 5~15h under part.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（4）The phosphorus source is phosphoric acid；Aluminium
Source can be one or more in aluminium isopropoxide, boehmite, aluminum sulfate, aluminium chloride and aluminum nitrate；Silicon source can be just
It is one or more in silester, White Carbon black, silica gel；Template is any one of ethylenediamine, triethylamine, morpholine.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（4）Middle phosphorus source, silicon source, silicon source, water
Mol ratio with template is preferably 0.3~1.5P：0.2~1.5SiO2：A12O3：20~100H2O：0.5~1.5 template
Agent.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, with step（4）A1 in middle silicon source2O3Weight
On the basis of, ZSM-12 molecular sieves and A1 in silicon source2O3Mass ratio be 0.3~1.5, preferably 0.5~1.2.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（4）Described in crystallization temperature
It is 150~240 DEG C, preferably 160~230 DEG C；Reaction time is 15~100h, preferably 20~90h.
In the synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention, step（4）Described in separation and washing
Be routine operation well known to those skilled in the art, if detached the method that can take filtering, washing generally refer to spend from
Sub- water washing.Generally include separating for several times and washing operation, generally 1~6 time.Drying condition is usually in 100~140 DEG C of items
Dry 5~15h under part.
The absorption that SAPO-34/ZSM-12 composite molecular screens provided by the invention may be used as gas, liquid mixture detaches
Agent can also be used as the carrier or acidic catalyst component of catalyst, especially in hydrocarbons hydrogenation cracking, hydroisomerization, alkane
In the reactions such as aromatisation, alkylation and transalkylation.
Compared with prior art, SAPO-34/ZSM-12 composite molecular screens provided by the invention and synthetic method have with
Lower advantage：
（1）The SAPO-34/ZSM-12 composite molecular screens that the present invention synthesizes have high-crystallinity, the composite molecular screen
Nuclear phase ZSM-12 molecular sieves have the characteristics that low silica-alumina ratio, and can synthesize low silica-alumina ratio within the scope of ultralow silica alumina ratio
Beta/EU-1 composite molecular screens.The molecular sieve has higher sour density, has higher catalysis anti-in certain catalysis reaction
Answer efficiency.
（2）The synthesis of nuclear phase ZSM-12 molecular sieves generally requires in synthetic system in SAPO-34/ZSM-12 composite molecular screens
Sial element be in high silica alumina ratio state, otherwise can not synthesize ZSM-12 molecular sieves.The conjunction of ZSM-12 molecular sieves of the present invention
At in method, it is allowed to aluminum nitrate roasting to be decomposed into a kind of inert aluminium oxide, this special inert alumina can be in ZSM-
Strong inertia is shown in 12 Crystallization of Zeolite reaction process, i.e., relative to step（2）Described in common silicon source can delay
Crystallization is participated in, crystallization can be made to be divided into two stages, first stage in this way：Step（2）Described in common silicon source
It is first reacted with other raw materials, generates ZSM-12 molecular sieve nucleus；Second stage：Wait for step（2）And step（3）Described in it is common
After silicon source consumption completely, special aluminium oxide can just participate in reacting, and be slowly to release aluminium species, can ensure in this way
The sial element that can be utilized during entire crystallization maintains a high silica alumina ratio level always.Be conducive to ZSM-12 in this way
The growth of molecular sieve, and the generation of impurity crystal can be inhibited, it is possible to it is closed in the case of low silica-alumina ratio raw material proportioning
At the low silica-alumina ratio ZSM-12 molecular sieves for going out high-purity.Again using low silica-alumina ratio ZSM-12 molecular sieves as nuclear phase, synthesize highly crystalline
The SAPO-34/ZSM-12 composite molecular screens of degree.
（3）The step of the method for the present invention（3）It is middle that suitable water is added into reaction system, step can be substantially reduced（2）
The viscosity of half obtained crystallization product, plays diluting effect, greatly improves dispersion degree of the inert alumina in half crystallization product,
Prevent the product crystallinity caused by stock dispersion unevenness from reducing the generation with stray crystal.
（4）Step in the method for the present invention（2）Described in template be relatively expensive template, have higher structure
Guiding role, in step（2）Described in crystallization process in be easy to form the nucleus of molecular sieve.Step（3）Described in second
Template is relatively inexpensive template, it may have structure-directing effect, in step（3）Described in crystallization process in can promote
Into the synthesis of molecular sieve, expensive template is substituted, reduces synthesis cost.
Description of the drawings
Fig. 1 is the XRD spectra for the SAPO-34/ZSM-12 composite molecular screens that embodiment 1 obtains.
Specific implementation mode
The synthetic method of SAPO-34/ZSM-12 composite molecular screens of the present invention is given in detail below by specific embodiment
Description, but be not limited to embodiment.
Embodiment 1
16g aluminum nitrates are placed in high temperature furnace first, 3h is roasted at 500 DEG C, obtains aluminium oxide.Then 0.6g hydroxides are taken
Sodium, 0.5g sodium aluminates, 4g methyl triethyl ammonium chlorides are placed in 50mL distilled water, and stirring is until all dissolvings, then to add 9g white
Carbon black is fitted into 160 DEG C of crystallization 12h in reactor.50mL distilled water, 2.5g tetraethylammonium bromides and aluminium oxide are added, is stirred
30min；Then the distilled water that 90mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 160 DEG C of crystallization in baking oven
90h.Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, obtains ZSM-12 molecular sieves.
It takes 11g aluminium isopropoxides to be dissolved in 45 mL distilled water, stirs 30 min.It is subsequently added into 4.6mL phosphoric acid, stirring 30
min.5mL ethyl orthosilicates are added, 30 min are stirred.Then 4mL ethylenediamines are added, stir 30min.Then 8 g steps are added
Suddenly（1）The ZSM-12 molecular sieves of preparation stir 30 min；It is then charged into closed reactor, 200 DEG C of crystallization 50 in baking oven
h.Then obtained product is washed with distilled water 4 times to neutrality, then dry 12h, gained sample are compiled under the conditions of 120 DEG C
Number CL1, gained sample is as shown in Figure 1, be SAPO-34/ZSM-12 composite molecular screens.
Embodiment 2
10g aluminum nitrates are placed in high temperature furnace first, 2h is roasted at 550 DEG C, obtains aluminium oxide.Then 0.7g hydrogen-oxygens are taken
Change sodium, 0.45g sodium aluminates, 3.4g methyl triethyl ammonium chlorides to be placed in 50mL distilled water, stirring is until all dissolve, then add
9g silica gel is fitted into 165 DEG C of crystallization 10h in reactor.50mL distilled water, 2.5g tetraethylammonium bromides and aluminium oxide are added, is stirred
Mix 30min；Then the distilled water that 90mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 165 DEG C of crystalline substances in baking oven
Change 100h.Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, obtains ZSM-12 molecules
Sieve.
It takes 9g aluminium isopropoxides to be dissolved in 45 mL distilled water, stirs 30 min.It is subsequently added into 4mL phosphoric acid, stirring 30
min.5mL ethyl orthosilicates are added, 30 min are stirred.Then 4mL ethylenediamines are added, stir 30min.Then 8 g steps are added
Suddenly（1）The ZSM-12 molecular sieves of preparation stir 30 min；It is then charged into closed reactor, 210 DEG C of crystallization 50 in baking oven
h.Then obtained product is washed with distilled water 4 times to neutrality, then dry 12h, gained sample are compiled under the conditions of 120 DEG C
Number CL1, gained sample is as shown in Figure 1, be SAPO-34/ZSM-12 composite molecular screens.
Embodiment 3
12g aluminum nitrates are placed in high temperature furnace first, 2.5h is roasted at 700 DEG C, obtains aluminium oxide.Then 0.6g hydrogen is taken
Sodium oxide molybdena, 0.25g aluminum nitrates, 4g methyl triethyl ammonium chlorides are placed in 50mL distilled water, and stirring is until all dissolve, then add
8.5g white carbons are fitted into 160 DEG C of crystallization 12h in reactor.Add 50mL distilled water, 1.8g tetraethylammonium bromides and oxidation
Aluminium stirs 30min；Then the distilled water that 85mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 160 in baking oven
DEG C crystallization 90h.Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, obtains ZSM-12 points
Son sieve.
It takes 15g aluminium isopropoxides to be dissolved in 40 mL distilled water, stirs 30 min.It is subsequently added into 5mL phosphoric acid, stirring 30
min.5mL ethyl orthosilicates are added, 30 min are stirred.Then 4mL ethylenediamines are added, stir 30min.Then 7 g steps are added
Suddenly（1）The ZSM-12 molecular sieves of preparation stir 30 min；It is then charged into closed reactor, 195 DEG C of crystallization 70 in baking oven
h.Then obtained product is washed with distilled water 4 times to neutrality, then dry 12h, gained sample are compiled under the conditions of 120 DEG C
Number CL3 is SAPO-34/ZSM-12.
Embodiment 4
17g aluminum nitrates are placed in high temperature furnace first, 2h is roasted at 580 DEG C, obtains aluminium oxide.Then 0.6g hydroxides are taken
Sodium, 0.3 aluminum sulfate, 3g methyl triethyl ammonium chlorides are placed in 50mL distilled water, and stirring is until all dissolve, then add 7g hard charcoals
It is black, it is fitted into 155 DEG C of crystallization 12h in reactor.50mL distilled water, 3g tetraethylammonium bromides and aluminium oxide are added, is stirred
30min；Then the distilled water that 90mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 155 DEG C of crystallization in baking oven
95h.Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, obtains ZSM-12 molecular sieves.
It takes 10g aluminium isopropoxides to be dissolved in 45 mL distilled water, stirs 30 min.It is subsequently added into 4.6mL phosphoric acid, stirring 30
min.4mL ethyl orthosilicates are added, 30 min are stirred.Then 4mL ethylenediamines are added, stir 30min.Then 8 g steps are added
Suddenly（1）The ZSM-12 molecular sieves of preparation stir 30 min；It is then charged into closed reactor, 200 DEG C of crystallization 80 in baking oven
h.Then obtained product is washed with distilled water 4 times to neutrality, then dry 12h, gained sample are compiled under the conditions of 120 DEG C
Number CL4 is SAPO-34/ZSM-12.
Comparative example 1
Take 0.6g sodium hydroxides, 0.5g sodium aluminates, 16g aluminum nitrates, 4g methyl triethyl ammonium chloride and 2.5g tetrem bromides
Change ammonium to be placed in 50mL distilled water, stirring is up to all dissolvings, then adds 7.5g white carbons, and confined reaction is packed into after stirring evenly
In kettle, 180 DEG C of crystallization 55h in baking oven.Obtained product is washed with distilled water 4 times to neutral, 120 DEG C of dry 12h.
It takes 11g aluminium isopropoxides to be dissolved in 45 mL distilled water, stirs 30 min.It is subsequently added into 4.6mL phosphoric acid, stirring 30
min.5mL ethyl orthosilicates are added, 30 min are stirred.Then 4mL ethylenediamines are added, stir 30min.It is subsequently added on 7g and walks
Obtained solid matter stirs 30 min.It is then charged into closed reactor, 200 DEG C of 50 h of crystallization in baking oven.Then will
Obtained product is washed with distilled water 4 extremely neutrality, then dry 12h, gained sample number into spectrum CL5, institute under the conditions of 120 DEG C
It is P type zeolite and unformed substance to obtain sample, can not synthesize SAPO-34/ZSM-12 composite molecular screens.
Comparative example 2
16g aluminum nitrates are placed in high temperature furnace first, 3h is roasted at 500 DEG C, obtains aluminium oxide.Then 0.6g hydroxides are taken
Sodium, 0.5g sodium aluminates, 4g methyl triethyl ammonium chlorides are placed in 50mL distilled water, and stirring is until all dissolvings, then to add 9g white
Carbon black is fitted into 160 DEG C of crystallization 12h in reactor.2.5g tetraethylammonium bromides and aluminium oxide are added, 30min is stirred；Then it fills
Enter in closed reactor, 180 DEG C of crystallization 50h in baking oven.To neutrality, then obtained product is washed with distilled water 4 times
Dry 12h at 120 DEG C.
It takes 11g aluminium isopropoxides to be dissolved in 45 mL distilled water, stirs 30 min.It is subsequently added into 4.6mL phosphoric acid, stirring 30
min.5mL ethyl orthosilicates are added, 30 min are stirred.Then 4mL ethylenediamines are added, stir 30min.It is subsequently added on 7g and walks
Obtained solid matter stirs 30 min.It is then charged into closed reactor, 200 DEG C of 50 h of crystallization in baking oven.Then will
Obtained product is washed with distilled water 4 times to neutrality, and then dry 12h under the conditions of 120 DEG C, gained sample number into spectrum are CL6,
Gained sample is SAPO-34/ZSM-12 composite molecular screens, but the crystallinity of sample is very low, can not synthesize high-crystallinity
SAPO-34/ZSM-12 composite molecular screens.
Comparative example 3
16g aluminum nitrates are placed in high temperature furnace first, 3h is roasted at 900 DEG C, obtains aluminium oxide；Then 0.6g hydroxides are taken
Sodium, 0.5g sodium aluminates, 4g methyl triethyl ammonium chlorides are placed in 50mL distilled water, and stirring is until all dissolvings, then to add 9g white
Carbon black is fitted into 160 DEG C of crystallization 12h in reactor.50mL distilled water, 2.5g tetraethylammonium bromides and aluminium oxide are added, is stirred
30min；Then the distilled water that 90mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 160 DEG C of crystallization in baking oven
90h.Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C.
It takes 11g aluminium isopropoxides to be dissolved in 45 mL distilled water, stirs 30 min.It is subsequently added into 4.6mL phosphoric acid, stirring 30
min.5mL ethyl orthosilicates are added, 30 min are stirred.Then 4mL ethylenediamines are added, stir 30min.It is subsequently added on 7g and walks
Obtained solid matter stirs 30 min.It is then charged into closed reactor, 200 DEG C of 50 h of crystallization in baking oven.Then will
Obtained product is washed with distilled water 4 times to neutrality, and then dry 12h under the conditions of 120 DEG C, gained sample number into spectrum are CL7,
Gained sample is crystalline alumina and other kinds of crystalloids, can not synthesize SAPO-34/ZSM-12 composite molecular screens.
Table 1 is the property of embodiment and comparative example products therefrom
Note：It is reference that the relative crystallinity that table 1 is given, which is with the crystallinity of CL1,.
Claims (21)
1. a kind of SAPO-34/ZSM-12 composite molecular screens, the composite molecular screen have simultaneously ZSM-12 molecular sieves crystalline phase and
The weight ratio of SAPO-34 molecular sieve crystalline phases, ZSM-12 molecular sieves and SAPO-34 molecular sieves in the composite molecular screen is 1：
0.2~2, the oxide silicon al mole ratio of the ZSM-12 molecular sieves is 9~22, the specific surface area 260~800 of composite molecular screen
m2/g；0.2~0.7 mmol/g of total acid content of composite molecular screen.
2. SAPO-34/ZSM-12 composite molecular screens described in accordance with the claim 1, it is characterised in that：The ZSM-12 molecular sieves
Oxide silicon al mole ratio be 10~20.
3. the synthetic method of SAPO-34/ZSM-12 composite molecular screens as claimed in claim 1 or 2, includes the following steps：
（1）Aluminum nitrate is roasted into 1~5h at 450~700 DEG C, obtains aluminium oxide；
（2）By inorganic base, silicon source, silicon source, water and template MTEA according to 1~8Na of molar ratio2O:25~55SiO2:A12O3:600
~2000H2O:The ratio of 2~25MTEA mixes, and silica-alumina gel is obtained after stirring evenly, be then charged into reactor in 140~
2~20h of crystallization at 220 DEG C；
（3）By step（1）Obtained aluminium oxide and step（2）Obtained reactant mixing, and the second template and water is added, it stirs
Mix uniformly after a certain amount of water is evaporated at 80~150 DEG C, be then charged into reactor, at 140~220 DEG C crystallization 24~
130h separating, washing and is dried to obtain ZSM-12 molecular sieves successively；
（4）By phosphorus source, silicon source, silicon source, water and template M according to 0.2~1.8P of mol ratio：0.15~1.8SiO2：A12O3：
15~120H2O：The ratio of 0.4~1.7M is uniformly mixed, and step is then added（3）Obtained ZSM-12 molecular sieves, in 150~
15~100h of crystallization at 240 DEG C, last separating, washing, drying and roasting obtain SAPO-34/ ZSM-12 composite molecular screens.
4. according to the method for claim 3, it is characterised in that：Step（1）Described in calcination temperature be 500~600 DEG C,
Roasting time is 1.5~4h.
5. according to the method for claim 3, it is characterised in that：Step（2）Described in inorganic base be NaOH, KOH, LiOH
In it is one or more；Silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source be White Carbon black,
It is one or more in silica gel, Ludox or waterglass；Template is methyl triethyl ammonium chloride（MTEA）.
6. according to the method for claim 3, it is characterised in that：Step（2）Described in inorganic base, silicon source, silicon source, water and
The mol ratio of template MTEA is 1.5~7Na2O:30~50SiO2:A12O3:800~1800H2O:4~20 MTEA.
7. according to the method for claim 3, it is characterised in that：Step（2）Described in crystallization be brilliant at 170~200 DEG C
Change 3~16h.
8. according to the method for claim 3, it is characterised in that：Step（3）Described in aluminium oxide and step（2）Described in
The molar ratio of silicon source is 15~1SiO2:A12O3。
9. according to the method described in claim 3 or 8, it is characterised in that：Step（3）Described in aluminium oxide and step（2）In
The molar ratio of the silicon source is 10~2SiO2:A12O3。
10. according to the method for claim 3, it is characterised in that：Step（3）Described in the second template be tetraethyl bromination
Ammonium, etamon chloride, second template and step（2）In template molar ratio be 0.5~2.
11. according to the method described in claim 3 or 10, it is characterised in that：Step（3）Described in the second template be tetraethyl
Ammonium bromide, etamon chloride, second template and step（2）In template molar ratio be 0.8~1.5.
12. according to the method for claim 3, it is characterised in that：Step（3）Described in addition water volume and step
（2）Described in water volume ratio be 0.5~1.5.
13. according to the method described in claim 3 or 12, it is characterised in that：Step（3）Described in addition water volume with
Step（2）Described in water volume ratio be 0.8~1.2.
14. according to the method for claim 3, it is characterised in that：Step（3）Described in need to evaporate quantitative water, steam
After hair falls water, inorganic base, silicon source, silicon source, the molar ratio of water and template are 1~8Na2O:25~55SiO2:A12O3:50~
120H2O:2~25 MTEA.
15. according to the method described in claim 3 or 14, it is characterised in that：Step（3）Described in need to evaporate it is quantitative
Water, after evaporating water, inorganic base, silicon source, silicon source, the molar ratio of water and template are 1.5~7Na2O:30~50SiO2:
A12O3:60~100H2O:4~20 MTEA.
16. according to the method for claim 3, it is characterised in that：Step（3）Described in evaporating temperature be 90~140 DEG C；It is brilliant
Turn to 30~110h of crystallization at 150~210 DEG C.
17. according to the method for claim 3, it is characterised in that：Step（4）The phosphorus source is phosphoric acid；Silicon source is isopropyl
It is one or more in aluminium alcoholates, boehmite, aluminum sulfate, aluminium chloride and aluminum nitrate；Silicon source be ethyl orthosilicate, White Carbon black,
It is one or more in silica gel；Template is any one of ethylenediamine, triethylamine, morpholine.
18. according to the method for claim 3, it is characterised in that：Step（4）Middle phosphorus source, silicon source, silicon source, water and template
Mol ratio be 0.3~1.5P：0.2~1.5SiO2：A12O3：20~100H2O：0.5~1.5 template.
19. according to the method for claim 3, it is characterised in that：With step（4）A1 in middle silicon source2O3On the basis of weight,
ZSM-12 molecular sieves and A1 in silicon source2O3Mass ratio be 0.3~1.5.
20. according to the method described in claim 3 or 19, it is characterised in that：With step（4）A1 in middle silicon source2O3Weight is base
Standard, ZSM-12 molecular sieves and A1 in silicon source2O3Mass ratio be 0.5~1.2.
21. according to the method for claim 3, it is characterised in that：Step（4）Described in crystallization temperature be 160~230
℃；Reaction time is 20~90h.
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