CN106946267B - A kind of EU-1 molecular sieve and its synthetic method - Google Patents
A kind of EU-1 molecular sieve and its synthetic method Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention discloses a kind of EU-1 molecular sieve and its synthetic method, the crystal structure of the EU-1 molecular sieve is typical EUO structure.The EU-1 Zeolite synthesis method is to mix inorganic base, silicon source, silicon source, template and water, stirs into silica-alumina gel and crystallization certain time；It is subsequently added into water, the second template and aluminium oxide to stir evenly, EU-1 molecular sieve is then obtained after hydrothermal crystallizing.The EU-1 composite molecular screen of the method for the present invention synthesis is low silica-alumina ratio zeolite, and crystallinity 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 EU-1 molecular sieve and its synthetic method, specifically a kind of low silica-alumina ratio EU-1 molecular sieve
Synthetic method, belong to molecular sieve catalytic material synthesis field.
Background technique
Zeolite molecular sieve is a kind of important industrial catalyst and catalyst carrier, is most crucial in catalytic reaction process
Unit.Zeolite molecular sieve is a kind of metastable crystal, its physicochemical properties such as silica alumina ratio, crystalline size in crystallography
Change with pattern meeting because of the difference of synthetic method.And these physico-chemical properties influence and adjust the catalytic activity of zeolite.
Therefore the zeolite for synthesizing different physico-chemical properties can just can satisfy the demand of different catalysis reactions.
A kind of synthetic method often defines raw material type, raw material proportioning range, the synthesis conditions such as crystallization temperature, time.
So the variation range of the physico-chemical parameters such as the crystal morphology of zeolite product, size, silica alumina ratio is just limited by synthetic method, no
It may be without limitation arbitrarily variation.Therefore, there is low silica-alumina ratio, high silica alumina ratio, big to synthesize that conventional method can not synthesize
The zeolite product of the special natures such as crystal grain or little crystal grain just needs to develop special synthesizing mean.
Such as CN101096275A, a kind of synthetic method of richness aluminium Beta zeolite disclose a kind of synthesis of Beta zeolite
Method.Its synthesis step is: 1. impregnate silicon source with the aqueous solution containing silicon source or acid solution, stirring to solidifying, with or do not have to
Aging is dehydrated after AMMONIA TREATMENT, after grinding, is roasted at 600~1400 DEG C, is obtained silicon and aluminum source；2. again by tetraethyl ammonium sun
Ionic compound and hydrofluoric acid mixing evaporate partial moisture in normal pressure and under being not higher than 130 DEG C or vacuum condition；3. will
Silicon and aluminum source is added in the tetraethyl ammonium hydroxide and hydrofluoric acid mixed solution of concentration, then obtained reaction mixture is carried out hydro-thermal crystalline substance
Change and recycles crystallization product.Although the patent can synthesize the Beta zeolite of low silica-alumina ratio, its synthesis process is more numerous
It is trivial, and additionally to use to the disagreeableness fluorine ion of environment, not only increase cost, and pollute environment.
A kind of CN101096274A, preparation method of richness aluminium Beta zeolite, discloses a kind of synthetic method of Beta zeolite.
Its synthesis step is: silicon source and silicon source are prepared silica-alumina cogels in the presence of hydrolytic reagent by 1., are crushed after aging and roasting
As silicon and aluminum source；2. then silicon and aluminum source to be added to the solution being made of tetraethylammonium cation, ammonium ion, fluorine ion and water
In, crystallization simultaneously recycles crystallization product and obtains zeolite.Although the patent can synthesize the Beta zeolite of low silica-alumina ratio, volume
Outer use not only increases cost to the disagreeableness fluorine ion of environment, and pollutes environment.
CN1086791A, directing agent method synthesize Beta zeolite, disclose a kind of synthetic method of Beta zeolite, synthesis
Beta zeolite also belongs to low silica-alumina ratio zeolite.Being mainly characterized by of the patent synthesizes Beta zeolite using directed agents.It is oriented to
Agent is dissolved in tetraethyl ammonium hydroxide template and sodium hydrate aqueous solution with aluminium salt, and active silica is added and leads to prepare
To agent, directed agents formula range are as follows: SiO2/Al2O3=20~120, TEAOH/SiO2=0.2~0.5, Na2O/SiO2=
0.40~0.10, H2O/SiO2=7.5~25, the preparation temperature of directed agents is 15~70 DEG C, and Aging Temperature is 50~150 DEG C, is closed
When at zeolite, the volume ratio of added directed agents and synthesis material mixture is 0.5%~10%.
CN101723394A, a kind of nano-beta molecular sieve with low Si/Al ratio and preparation method thereof disclose a kind of low silicon Beta boiling
The synthetic method of stone.The patent is mainly characterized by using FAU molecular sieve as silicon source, and adjusts basicity and reduction with ammonium hydroxide
Na ion concentration.But primary raw material silicon source used in the patent is FAU molecular sieve, FAU molecular sieve is also to need hydrothermal crystallizing
Synthesis, it is prohibitively expensive compared to silicon sources, costs such as conventional sodium aluminate, aluminum sulfate.
There are also certain methods to synthesize other type zeolites with low silicon features, such as CN103601213A, low silica-alumina ratio
Nanometer sheet flowers shape mordenite molecular sieve preparation method, discloses a kind of method of zeolite.Its preparation process includes: by aluminium
In deionized water, to obtaining that silica solution is added in clear solution, obtained flat-white colloid is transferred to instead for source, alkali source dissolution
It answers and carries out hydro-thermal reaction in kettle, obtain low silica-alumina ratio mordenite molecular sieve.
A kind of CN102417190A, method that application activation silicon source prepares low silicon NaX zeolite, discloses a kind of low-silicon X-shaped
The method of zeolite.The patent be mainly characterized by preparation activation silicon source, the activation silicon source be added into common silicon source it is a certain amount of
Alkaline silicon source solution, make in common silicon source the high poly- oligomeric state silicate of state silicate depolymerization, and the generation in conjunction with aluminate
Effective sial acid group presoma and faujasite microcrystals.
Summary of the invention
There are existing low silicone zeolite molecular sieve some silica-rich zeolites not have unique physico-chemical property, therefore certain specific
Field has better application effect.But since zeolite molecular sieve is a kind of metastable crystal, its physico-chemical property is closed
It is by thermodynamic (al) limitation in principle at the restriction of method.When silica alumina ratio is too low, zeolite crystal handles energy level not
Stable state, therefore be very difficult to synthesize.Low silicone zeolite is not also overripened relative to the synthetic technology of silica-rich zeolite, therefore develops
The synthetic method of new low silicone zeolite just has important practical significance.
In view of the deficiencies of the prior art, the present invention provides a kind of EU-1 molecular sieve and its synthetic method, this method synthesis
EU-1 molecular sieve has the feature of low silica-alumina ratio, and whole preparation process is simple and easy, is suitble to industrialized production.
The present invention provides a kind of EU-1 molecular sieve, and the crystal structure of the EU-1 molecular sieve is typical EUO structure, is free of
Other impurity crystal, the EU-1 molecular sieve alumina silicon al mole ratio are 11~20, preferably 12~18, and crystal size is less than
200nm, 300 ~ 700 m of specific surface area2/g。
The present invention also provides a kind of synthetic methods of EU-1 molecular sieve recited above, comprising the following steps:
(1) aluminum nitrate is roasted to 1~5h at 450~700 DEG C, obtains aluminium oxide；
(2) by inorganic base, silicon source, silicon source, water and template (M) according to 0.5~8Na of molar ratio2O:25~80SiO2:
A12O3: 400~1800H2O:1~10(M) ratio mixing, be fitted into reactor the crystallization at 150~230 DEG C after mixing evenly
2~20h；
(3) aluminium oxide that step (1) obtains and the reactant that step (2) obtains are mixed, the second template is then added
And water, a certain amount of water is evaporated after being uniformly mixed at 80~150 DEG C, is reloaded into reactor at 150~230 DEG C
30~180h of crystallization, last separating, washing and is dried to obtain EU-1 molecular sieve.
In the synthetic method of EU-1 molecular sieve of the present invention, maturing temperature as described in step (1) is preferably 500~600 DEG C,
Calcining time is preferably 1.5~4h.
In the synthetic method of EU-1 molecular sieve of the present invention, inorganic base described in step (2) can be NaOH, KOH, LiOH
One of or it is a variety of；Source of aluminium is one of sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate or a variety of；The silicon source is
One of White Carbon black, silica gel, silica solution or waterglass are a variety of；Template (M) is hexamethylene bromide [(HM) OBr2]。
In the synthetic method of EU-1 molecular sieve of the present invention, inorganic base, silicon source, silicon source, water and template described in step (2)
Molar ratio be preferably 1~7Na2O:30~70SiO2: A12O3: 500~1300H2O:2~8(M).
In the synthetic method of EU-1 molecular sieve of the present invention, crystallization described in step (2) be at 150~230 DEG C crystallization 5~
12h。
In the synthetic method of EU-1 molecular sieve of the present invention, silicon source described in aluminium oxide described in step (3) and step (2)
Molar ratio be 15~1SiO2:A12O3, preferably 10~2SiO2:A12O3。
In the synthetic method of EU-1 molecular sieve of the present invention, the second template described in step (3) is tetraethylammonium bromide, the
The molar ratio of template is 0.5~2, preferably 0.8~1.5 in two templates and step (2).
In the synthetic method of EU-1 molecular sieve of the present invention, in the volume of the water of addition described in step (3) and step (2)
The volume ratio of the water is 0.5~1.5, preferably 0.8~1.2.
In the synthetic method of EU-1 molecular sieve of the present invention, step needs to evaporate a certain amount of water described in (3), evaporates
After a certain amount of water, inorganic base, silicon source, silicon source, the molar ratio of water and template should be maintained at 0.5~8Na2O:25~80SiO2:
A12O3: 40~200H2O:1~10 [(HM) OBr2], preferably 1~7Na2O:30~70SiO2: A12O3: 60~150H2O:2~8
[(HM)OBr2]。
In the synthetic method of EU-1 molecular sieve of the present invention, evaporating temperature described in step (3) is 80~140 DEG C.
In the synthetic method of EU-1 molecular sieve of the present invention, crystallization described in step (3) is brilliant preferably at 180~220 DEG C
Change 48~144h.
In the synthetic method of EU-1 molecular sieve of the present invention, the separation and washing are well known to those skilled in the art
Routine operation, as separated the method that can take filtering, washing generally refers to be washed with deionized.Generally include separating for several times
And washing operation, generally 1~6 time.Drying condition is usually dry 5~15h under the conditions of 100~140 DEG C.
EU-1 molecular sieve provided by the invention may be used as the adsorbent of gas, liquid mixture separation, can also be used as
The carrier or acidic catalyst component of catalyst, can be widely applied to petrochemical industry.
Compared with prior art, EU-1 molecular sieve provided by the invention and synthetic method have the advantage that
(1) the EU-1 molecular sieve that the present invention synthesizes has the characteristics that high-crystallinity and low silica-alumina ratio, and can be ultralow
Synthesize low silica-alumina ratio EU-1 molecular sieve within the scope of silica alumina ratio.The molecular sieve has higher sour density, reacts in certain catalysis
In have higher catalysis reaction efficiency.
(2) synthesis of EU-1 molecular sieve generally requires the sial element in synthetic system to be in high silica alumina ratio state, otherwise
EU-1 molecular sieve can not be synthesized.In the synthetic method of EU-1 molecular sieve of the present invention, it is allowed to aluminum nitrate roasting to be decomposed into one kind
Inert aluminium oxide, this special inert alumina can show strong lazy in EU-1 Crystallization of Zeolite reaction process
Property, i.e., participation crystallization can be delayed relative to common silicon source described in step (2), crystallization can be made to be divided into two in this way
In a stage, the first stage: common silicon source described in step (2) is first reacted with other raw materials, generates EU-1 molecular sieve nucleus；The
Two-stage: the common silicon source described in the step (2) and step (3) run out of it is complete after, special aluminium oxide can just participate in reacting,
And it is slowly to release aluminium species, can guarantees that the sial element that can be utilized during entire crystallization is tieed up always in this way
It holds in a high silica alumina ratio level.Be conducive to the growth of EU-1 molecular sieve in this way, and the generation of impurity crystal can be inhibited, institute
The low silica-alumina ratio EU-1 molecular sieve of high-purity can be synthesized in the case where low silica-alumina ratio raw material proportioning.
(3) suitable water is added into reaction system in the step of the method for the present invention (3), step (2) can be substantially reduced
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 due to caused by stock dispersion unevenness from reducing the generation with stray crystal.
(4) template described in step (2) is relatively expensive template, structure with higher in the method for the present invention
Guiding role, the nucleus of molecular sieve easy to form in the crystallization process described in step (2).Second described in step (3)
Template is relatively inexpensive template, it may have structure-directing effect can promote in the crystallization process in step (3)
Into the synthesis of molecular sieve, expensive template is substituted, reduces synthesis cost.
Detailed description of the invention
Fig. 1 is the XRD spectra for the EU-1 molecular sieve that embodiment 1 obtains.
Specific embodiment
It is described in detail below by synthetic method of the specific embodiment to EU-1 molecular sieve of the present invention, but not office
It is limited to embodiment.
Embodiment 1
16g aluminum nitrate is placed in high temperature furnace first, in 500 DEG C of roasting 3h, obtains aluminium oxide.Then 1.11g hydrogen-oxygen is taken
Change sodium, 0.82g sodium aluminate, 6g hexamethylene bromide are placed in 50mL distilled water, stirring is until all dissolutions, then to add 8.3g white
Carbon black is fitted into 190 DEG C of crystallization 7h in reactor.50mL distilled water, 4g tetraethylammonium bromide 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, 190 DEG C of crystallization in baking oven
72h.Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, gained sample number into spectrum CL1, institute
Sample is obtained as shown in Figure 1, being pure EU-1 molecular sieve, is free of other impurity.
Embodiment 2
10g aluminum nitrate is placed in high temperature furnace first, 2h is roasted at 550 DEG C, obtains aluminium oxide.Then 1.11g hydrogen is taken
Sodium oxide molybdena, 0.5g sodium aluminate, 5g hexamethylene bromide are placed in 50mL distilled water, and stirring is until all dissolve, then add 8.3g
Silica gel is fitted into 190 DEG C of crystallization 6h in reactor.50mL distilled water, 3g tetraethylammonium bromide and aluminium oxide are added, is stirred
30min；Then the distilled water that 85mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 190 DEG C of crystallization in baking oven
65h.Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, gained sample number into spectrum CL2 are
EU-1 molecular sieve.
Embodiment 3
12g aluminum nitrate is placed in high temperature furnace first, 2.5h is roasted at 700 DEG C, obtains aluminium oxide.Then 0.8g hydrogen is taken
Sodium oxide molybdena, 0.25g aluminum nitrate, 6g hexamethylene bromide are placed in 50mL distilled water, and stirring is until all dissolve, then add 8.3g
White carbon black is fitted into 200 DEG C of crystallization 7h in reactor.60mL distilled water, 4g tetraethylammonium bromide and aluminium oxide are added, is stirred
30min；Then the distilled water that 80mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 200 DEG C of crystallization in baking oven
80h.Obtained product being washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, gained sample number into spectrum is CL3,
For EU-1 molecular sieve.
Embodiment 4
17g aluminum nitrate is placed in high temperature furnace first, in 580 DEG C of roasting 2h, obtains aluminium oxide.Then 0.3g hydroxide is taken
Sodium, 0.3 aluminum sulfate, 5.5g hexamethylene bromide are placed in 50mL distilled water, and stirring is until all dissolve, then add 7.5g hard charcoal
It is black, it is fitted into 210 DEG C of crystallization 5h in reactor.35mL distilled water, 3g tetraethylammonium bromide and aluminium oxide are added, 30min is stirred；
Then the distilled water that 75mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor, 210 DEG C of crystallization 50h in baking oven.It will
Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, and it is EU-1 that gained sample number into spectrum, which is CL4,
Molecular sieve.
Comparative example 1
Take 1.11g sodium hydroxide, 0.82g sodium aluminate, 16g aluminum nitrate, 6g hexamethylene bromide and 4g tetraethylammonium bromide
It is placed in 50mL distilled water, stirring is up to all dissolutions, then adds 8.3g white carbon black, is packed into closed reactor after mixing evenly
In, 190 DEG C of crystallization 79h in baking oven.Obtained product is washed with distilled water 4 times to neutral, 120 DEG C of dry 12h, gained
Sample number into spectrum CL5, gained sample are P type zeolite, can not synthesize EU-1 molecular sieve.
Comparative example 2
16g aluminum nitrate is placed in high temperature furnace first, in 500 DEG C of roasting 3h, obtains aluminium oxide；Then 1.11g hydrogen-oxygen is taken
Change sodium, 0.82g sodium aluminate, 6g hexamethylene bromide are placed in 50mL distilled water, stirring is until all dissolutions, then to add 8.3g white
Carbon black is fitted into 190 DEG C of crystallization 7h in reactor.4g tetraethylammonium bromide and aluminium oxide are added, 30min is stirred；It is then charged into
In closed reactor, 190 DEG C of crystallization 72h in baking oven.Obtained product is washed with distilled water 4 times to neutral, then 120
Dry 12h, gained sample number into spectrum CL6, are EU-I molecular sieve, but crystallinity is lower at DEG C.
Comparative example 3
16g aluminum nitrate is placed in high temperature furnace first, in 900 DEG C of roasting 3h, obtains aluminium oxide；Then 1.11g hydrogen-oxygen is taken
Change sodium, 0.82g sodium aluminate, 6g hexamethylene bromide are placed in 50mL distilled water, stirring is until all dissolutions, then to add 8.3g white
Carbon black is fitted into 190 DEG C of crystallization 7h in reactor.50mL distilled water, 4g tetraethylammonium bromide 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, 190 DEG C of crystallization in baking oven
72h.Obtained product being washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C, gained sample number into spectrum is CL7,
Gained sample is crystalline alumina, can not synthesize EU-I molecular sieve.
Comparative example 4
1.11g sodium hydroxide, 0.82g sodium aluminate, 6g hexamethylene bromide is taken to be placed in 50mL distilled water, stirring is until complete
Portion's dissolution, then 8.3g white carbon black is added, it is fitted into 190 DEG C of crystallization 7h in reactor.Add 50mL distilled water, 4g tetraethyl bromination
Ammonium and 16g aluminum nitrate stir 30min；Then the distilled water that 90mL is evaporated under the conditions of 140 DEG C, is fitted into closed reactor,
190 DEG C of crystallization 72h in baking oven.Obtained product is washed with distilled water 4 times to neutral, then dry 12h at 120 DEG C,
Gained sample number into spectrum CL8, gained sample are P type zeolite, can not synthesize EU-1 molecular sieve.
Table 1 is the property of embodiment and comparative example products therefrom
Note: the relative crystallinity that table 1 is given is with the crystallinity of CL1 for reference.
Claims (19)
1. a kind of synthetic method of EU-1 molecular sieve, comprising the following steps:
(1) aluminum nitrate is roasted to 1~5h at 450~700 DEG C, obtains aluminium oxide；
(2) by inorganic base, silicon source, silicon source, water and template (M) according to 0.5~8Na of molar ratio2O:25~80SiO2: A12O3:
400~1800H2The ratio of O:1~10M mixes, and is fitted into reactor 2~20h of crystallization at 150~230 DEG C after mixing evenly；
(3) aluminium oxide that step (1) obtains and the reactant that step (2) obtains are mixed, the second template and water are then added,
A certain amount of water is evaporated after being uniformly mixed at 80~150 DEG C, is reloaded into reactor the crystallization at 150~230 DEG C
30~180h, last separating, washing and is dried to obtain EU-1 molecular sieve.
2. according to the method for claim 1, it is characterised in that: maturing temperature as described in step (1) is 500~600 DEG C,
Calcining time is 1.5~4h.
3. according to the method for claim 1, it is characterised in that: inorganic base described in step (2) is NaOH, KOH, LiOH
One of or it is a variety of；Source of aluminium is one of sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate or a variety of；The silicon source is
One of White Carbon black, silica gel, silica solution or waterglass are a variety of；Template (M) is hexamethylene bromide.
4. according to the method for claim 1, it is characterised in that: inorganic base, silicon source, silicon source, water and mould described in step (2)
The molar ratio of plate agent is 1~7Na2O:30~70SiO2: A12O3: 500~1300H2O:2~8M.
5. according to the method for claim 1, it is characterised in that: crystallization described in step (2) is brilliant at 150~230 DEG C
Change 5~12h.
6. according to the method for claim 1, it is characterised in that: described in aluminium oxide described in step (3) and step (2)
The molar ratio of silicon source is 15~1SiO2:A12O3。
7. according to method described in claim 1 or 6, it is characterised in that: in aluminium oxide described in step (3) and step (2)
The molar ratio of the silicon source is 10~2SiO2:A12O3。
8. according to the method for claim 1, it is characterised in that: the second template described in step (3) is tetraethyl bromination
Ammonium.
9. according to the method for claim 1, it is characterised in that: mould in the second template described in step (3) and step (2)
The molar ratio of plate agent is 0.5~2.
10. according to method described in claim 1 or 9, it is characterised in that: the second template described in step (3) and step (2)
The molar ratio of middle template is 0.8~1.5.
11. according to the method for claim 1, it is characterised in that: the volume and step of the water of addition described in step (3)
(2) volume ratio of water described in is 0.5~1.5.
12. according to method described in claim 1 or 11, it is characterised in that: the volume of the water of addition described in step (3) with
The volume ratio of water described in step (2) is 0.8~1.2.
13. according to the method for claim 1, it is characterised in that: after evaporating a certain amount of water, inorganic base, silicon source, aluminium
The molar ratio in source, water and template is 0.5~8Na2O:25~80SiO2: A12O3: 40~200H2O:1~10M.
14. according to method described in claim 1 or 13, it is characterised in that: after evaporating a certain amount of water, inorganic base, silicon source,
The molar ratio of silicon source, water and template is 1~7Na2O:30~70SiO2: A12O3: 60~150H2O:2~8M.
15. according to the method for claim 1, it is characterised in that: evaporating temperature described in step (3) is 80~140 DEG C.
16. according to the method for claim 1, it is characterised in that: crystallization described in step (3) is brilliant at 180~220 DEG C
Change 48~144h.
17. a kind of EU-1 molecular sieve, it is characterised in that prepared using any method in claim 1-16.
18. EU-1 molecular sieve according to claim 17, it is characterised in that: the crystal structure of the EU-1 molecular sieve is allusion quotation
The EUO structure of type is free of other impurity crystal, and the EU-1 molecular sieve alumina silicon al mole ratio is 11~20, crystal size
Less than 200nm, 300 ~ 700 m of specific surface area2/g。
19. EU-1 molecular sieve according to claim 18, it is characterised in that: the EU-1 molecular sieve aluminium oxide sial mole
Than being 12~18.
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| CN109704356B (en) * | 2017-10-26 | 2021-05-11 | 中国石油化工股份有限公司 | Method for synthesizing EU-1 zeolite molecular sieve |
| CN111170333A (en) * | 2018-11-13 | 2020-05-19 | 中国科学院大连化学物理研究所 | Synthesis method of large-grain EU-1 molecular sieve |
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