CN107416859A - A kind of preparation method and application of step hole Beta molecular sieves - Google Patents
A kind of preparation method and application of step hole Beta molecular sieves Download PDFInfo
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- CN107416859A CN107416859A CN201710270575.9A CN201710270575A CN107416859A CN 107416859 A CN107416859 A CN 107416859A CN 201710270575 A CN201710270575 A CN 201710270575A CN 107416859 A CN107416859 A CN 107416859A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- C07C67/00—Preparation of carboxylic acid esters
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
A kind of preparation method and application of step hole Beta molecular sieves, belongs to molecular sieve preparation field.This method is kaolin or rectorite using sub-molten salt activation as whole silicon sources and part silicon source, under conditions of any organic formwork agent is not added, mineral after activation, alkali source, supplement silicon source, crystal seed and deionized water are well mixed according to a certain percentage, by step hydrothermal crystallizing synthesis with the compound step hole Beta molecular sieves of macropore micropore.Method advantage provided by the invention is, using the natural minerals of sub-molten salt activation as whole silicon sources and part silicon source, and organic formwork agent is not used completely in building-up process, not only significantly reduce the synthesis cost of Beta molecular sieves, considerably improve the green of molecular screen material production process, and the Beta molecular sieves of synthesis are the compound step Porous materials of macropore micropore, have higher relative crystallinity and BET specific surface area, therefore have preferable prospects for commercial application.
Description
Technical field
The invention belongs to molecular sieve preparation field, and in particular to a kind of preparation method of step hole Beta molecular sieves.
Background technology
Beta molecular sieves were synthesized first equal to 1967 by the Wadlinger of Mobil companies, its successful Composite Logo
The beginning in silica-rich zeolite epoch.Beta molecular sieves have unique pore passage structure, suitable acidity, and good Re Heshui
Heat endurance, it is a kind of important catalysis and sorbing material, is obtained in petroleum refining, petrochemical industry and catalyst preparation field
To widely applying.It is well known that tetraethyl ammonium hydroxide (TEAOH) is that current synthesis Beta molecular sieves are the most widely used
Template.But the use of organic formwork agent also brings the problem of many negative.First, the organic species as template, one
As price costly, and itself building-up process complex operation is cumbersome；Second, sieve synthesis procedure produces a large amount of waste water, by
In wherein containing a large amount of environmentally harmful organic formwork agents, so having to pass through effective processing can be only achieved discharge standard；
Third, in the Zeolite synthesis later stage, the general method using high-temperature roasting removes organic formwork agent, and this process not only needs
The substantial amounts of energy, and the heated oxidation Decomposition of organic species are consumed, can also discharge a large amount of pernicious gases (such as greenhouse gases), this
Outside, the subtractive process of organic formwork agent, caving in for skeleton structure of zeolite can also be caused, so as to reduce the utilizability of molecular sieve.
US 3308069 is reported using white carbon as silicon source, and sodium aluminate is silicon source, is made into slurries, in crystallizing kettle in
Crystallization 3 ~ 60 days at 75 ~ 200 DEG C, its raw material mol ratio in terms of oxide are：SiO2/Al2O3=10 ~ 200, TEAOH/SiO2
=0.1 ~ 1.0, Na2O/TEAOH=0 ~ 0.1, H2O/TEAOH=20~75.The patent discloses the synthesis side of Beta molecular sieves first
Method, but the dosage of organic formwork agent tetraethyl ammonium hydroxide is larger in this process and crystallization time is longer, synthesis cost is high.
In order to reduce the synthesis cost of Beta molecular sieves, many researchers are attempted using cheap non-tetraethyl ammonium hydroxide
Template.Such as：Using dimethyl benzylamine-benzyl halide (EP 159846), dibenzyl dimethylamine (US 4642226), two sub- second
Base triamine (US7704487B2) and relatively inexpensive tetraethyl ammonium halide (US 4847055) use composite mould plate agent system,
Such as TEAOH- diethanol amine (US 5139759).
Although the above method reduces the cost of molecular sieve, waste water is still suffered from building-up process, waste gas discharges
Problem.So the research work for reducing Beta Zeolite synthesis costs in recent years turns to from relatively inexpensive alternate template agent is found
Template-free method synthesis Beta molecular sieves.
Patent CN 101249968A have invented a kind of method of Template-free method synthesis Beta molecular sieves, using white carbon as silicon
Source, sodium aluminate are silicon source, by adding the Beta molecular sieve seeds after roasting into Primogel, in crystallizing kettle in 100 ~
Crystallization 12-24 hours at 180 DEG C, its raw material mol ratio in terms of oxide are：SiO2/Al2O3=31.4 ~ 40.3, Na2O/
SiO2=0.26 ~ 0.342, H2O/SiO2=13~50.Beta molecular sieve seeds SiO2/Al2O3Mol ratio is 22 ~ 25, Seed charge
For 5 ~ 20 wt% of silicon source.The invention, which breaches Beta Zeolite synthesis, must use the limitation of organic formwork agent, crystallization time
It is short.But the shortcomings of this method is narrow in the presence of synthesis phase region, and crystal seed range of choice is small.
Patent CN200610115385.1 reports a kind of method that Beta molecular sieves are prepared using kaolin as raw material, be with
The kaolin of acid treatment is then added into TEA as silicon and aluminum source+And Na+The aqueous solution in stir, in 120 ~ 185 DEG C
Hydrothermal condition under crystallization 26 ~ 60 hours.Its raw material mol ratio in terms of oxide is：SiO2/Al2O3=60 ~ 100, Na2O/SiO2=
0.019 ~ 0.095, TEAOH/SiO2>=0.03, H2O/SiO2=1.3~5.3.This method is reacted in super dense system, brilliant
The change time is short, and Beta molecular sieve crystallinities are high.But this method has still used substantial amounts of organic formwork agent, cause synthesis into
This is still higher.
Following discloses document also relates to the Template-free method study on the synthesis of Beta molecular sieves.
Open source literature (Chemistry of Materials 2008,20 (14), 4533-4535) reports first
The Beta molecular sieves introduced in the Primogel of organic-free template after roasting as crystal seed, realize Beta molecular sieves without mould
Plate synthesizes.They are using white carbon as silicon source, NaAlO2For the reunion state nanometer Beta molecular sieves (SiO after silicon source, roasting2/Al2O3
Mol ratio is 20 ~ 25) crystal seed is used as, the Primogel proportioning of synthetic system is 40SiO2:1Al2O3:10Na2O:570H2O, crystallization
Condition is crystallization 17 ~ 19 hours at 140 DEG C, and this method breaches Beta molecular sieves first must use the limit of organic formwork agent
System, crystallization time is short, significantly reduces the production cost of molecular sieve.
Hereafter, open source literature (Chemistry of Materials 2009,21 (18), 4184-4191) reports
Different material (is freeze-dried SiO without template system2Powder or Ludox are silicon source, aluminium isopropoxide is silicon source) Beta points of synthesis
During son sieve, it is crystal seed mainly to employ unfired nanometer Beta molecular screen primary powders, and Primogel proportioning is 25SiO2:0.25
~0.75Al2O3:7.5Na2O:375H2O, crystallization temperature scope are 100 ~ 125 DEG C.Author thinks that synthesis can only be in relatively low crystallization
At a temperature of (≤125 DEG C) progress, Beta molecular sieve product yields low (25-30%) and rich aluminium (7.8<SiO2/Al2O3<11), crystal grain
Degree has increased than crystal seed.
Open source literature (Chemistry An Asian Journal, 2010,5,2182-2191) reports one kind
The synthetic method of Beta molecular sieve Template-free methods, they are using white carbon as silicon source, NaAlO2For the Beta molecules after silicon source, roasting
Sieve as crystal seed, gel proportioning is SiO2/Al2O3=40 ~ 100, Na2O/SiO2=0.275 ~ 0.325, H2O/SiO2=25.Crystallization condition
For crystallization at 140 DEG C 30 ~ 70 hours, this method was successfully used as crystal seed, progress by the use of the Beta molecular sieves that Template-free method method synthesizes
Transmission of the single sintering crystal seed under Template-free method system, but the Beta molecular sieves synthesized by the document are still micropore material
Material.
Carrier of the step porous molecular sieve as active specy (metal, alloy, oxide), can effectively prevent these work
The aggregation that property species occur in preparation process, improves its decentralization；And the dual-active of preparation-obtained bifunctional catalyst
Property center (the activity itself position for supporting active specy and grade porous molecular sieve) preferably can be contacted with reactant, play collaboration
Effect.
In recent years, as what researcher was studied Beta Zeolite synthesis gradually gos deep into, by being introduced in synthesis
The hard mould agents such as carbon nanomaterial, organosilan and porous silicon carbide successfully synthesize with step hole Beta molecular sieves.Simultaneously
Open source literature (Angew Chem Int Edit, 2006,45 (19), 3090-3093) is reported with the poly- diformazan of polycation
Base diallyl ammonium chloride is that template successfully synthesizes the Beta molecular sieves with step hole.But used Jie/big casement
Plate agent is often difficult to obtain, not only expensive, and its subtractive process may also cause to cause framework of molecular sieve structure collapses, and
Disposal of pollutants is produced, is the process of a non-green.
In addition, synthesizing step hole Beta molecular sieves can also be by the removing micropore Beta molecular sieve of selectivity
Frame center's atom and form mesopore orbit.Open source literature (Microporous Mesoporous Materials 2008,
114,93) report and step hole Beta molecular sieves have been obtained using molten silicon method；Open source literature (Journal of
Catalysis 2014,312,46-57) report using NaOH and TBAOH processing Beta molecular sieves, obtain product after processing
There is the SiO of obvious mesopore orbit and product2/Al2O3Reduce.The advantages of this post treatment method is convenient, simple, but
Unmanageable formed mesoporous pore size, and post processing may damage to molecular sieve crystal skeleton, and produce substantial amounts of useless
Liquid discharges, and is also non-green process.
In summary, Template-free method synthesis step hole Beta molecular sieves are still the emphasis and hardly possible of current synthesis Beta molecular sieves
Point, if step hole can directly be synthesized under conditions of Template-free method, without post processing using cheap natural clay mineral as raw material
Beta molecular sieves, it certainly will will improve the green of its preparation process and the use of product while molecular sieve cost is reduced
Performance.
The content of the invention
In place of solving shortcoming and defect existing for prior art, melted it is an object of the invention to provide one kind using sub-
The kaolin of salt activation or the method for rectorite Template-free method synthesis Beta molecular sieves, and the Beta molecular sieves synthesized are big
The compound step Porous materials of hole-micropore, there is higher BET specific surface area (600-700 m2/g)。
For achieving the above object, concrete technical scheme of the invention is：
A kind of method of kaolin or rectorite green syt Beta molecular sieves using sub-molten salt activation, by sodium hydroxide, Asia
Natural minerals, supplement silicon source, crystal seed and the deionized water of fused salt activation are according to SiO2:Al2O3:Na2O:H2O=1:0.01~0.05:
0.2~0.35:8 ~ 20 molar ratio is well mixed, and Beta molecular sieves are then obtained after aging, hydrothermal crystallizing.
The SiO of Beta molecular sieve seeds2/Al2O3Mol ratio is 15 ~ 30:1, quality is added as synthetic system silicon source quality
1~10%.In the present invention, the Beta molecular sieves as crystal seed both can be commercially available Beta zeolites or be calcined or not
The laboratory synthesis Beta molecular sieves of roasting.
Currently preferred aging temperature is 50 ~ 80 DEG C, and ageing time is 2-24 h；Crystallization temperature is 110 ~ 160 DEG C, brilliant
The change time is 12 ~ 72 h.
The sub-molten salt activation of natural clay mineral of the present invention is the side provided according to CN201310217164.5
Prepared by method, specifically by natural clay mineral and sodium hydroxide solution according to 1:2~1:20 mass ratio is well mixed,
Then dried at 100 DEG C ~ 300 DEG C, products therefrom is the clay mineral after activating；Described natural clay mineral is kaolinite
Soil or rectorite；Wherein, it by sodium hydrate solid and water according to mass ratio is 1 that the sodium hydroxide solution, which is,:1~1:10 mixing
Form.
Supplement silicon source of the present invention is the one or more in white carbon, Ludox or waterglass.
Beta molecular sieves obtained by above-mentioned preparation method are the compound step Porous materials of macropore-micropore of high-crystallinity,
Its relative crystallinity is 80 ~ 120%, and specific surface area is 600 ~ 700 m2/g。
Beta molecular sieves synthesized by the present invention are used in the reaction of acetic acid and ethanol synthesizing ethyl acetate.Using fixed bed
Reactor successive reaction；The reaction temperature of acetic acid and ethanol synthesizing ethyl acetate is 100 ~ 150 DEG C, preferably 110-140 DEG C；Instead
It is 0.08 ~ 0.2MPa, preferably 0.09-0.15 MPa to answer pressure；The mol ratio of acetic acid and ethanol is 1:0.8~1:3, be preferably
1:0.9~1:2；Weight (hourly) space velocity (WHSV) is 0.8 ~ 2.0 h-1, preferably 0.9-1.5 h-1。
The beneficial effects of the invention are as follows：
1）The present invention can utilize good big of natural minerals synthetic crystallization degree in the range of complete Template-free method, wider silica alumina ratio
The compound step hole Beta molecular sieve products of hole-micropore, it is entirely avoided the removing of organic formwork agent pollutes to environment, real
The purpose of existing green syt Beta molecular sieves, while the destruction to framework of molecular sieve is it also avoid, so that the product tool of synthesis
There is higher BET specific surface area；
2）The step hole Beta molecular sieves of synthesis are applied in the esterification of acetic acid and ethanol by the present invention, achieve significant
Effect：Compared with commercially available Beta molecular sieves, under identical reaction conditions, the Beta molecular sieves synthesized by the present invention can make
6 ~ 15 percentage points of the conversion ratio raising of acetic acid, meanwhile, the selectivity of ethyl acetate improves 6 ~ 10 percentage points.
Brief description of the drawings
Fig. 1 is the XRD spectra of commercially available Beta molecular sieves；
Fig. 2 is the XRD spectra for the Beta molecular sieves that the embodiment of the present invention 1 synthesizes；
Fig. 3 is the N for the Beta molecular sieves that the embodiment of the present invention 1 synthesizes2Adsorption-desorption isothermal
Fig. 4 is the graph of pore diameter distribution for the Beta molecular sieves that the embodiment of the present invention 1 synthesizes；
Fig. 5, Fig. 6, Fig. 7, Fig. 8, Fig. 9 are respectively the XRD spectra for the Beta molecular sieves that the embodiment of the present invention 2 ~ 6 synthesizes.
Embodiment
For the further open rather than limitation present invention, below in conjunction with example, the present invention is described in further detail.
Comparative example 1
The relative crystallinity of synthetic sample is calculated as standard sample using commercially available Beta molecular sieves, its crystallinity is defined as
100%, the BET specific surface area of the molecular sieve is 520 m2/g。
This Beta molecular sieve is used in the reaction of acetic acid and ethanol synthesizing ethyl acetate, reacted in fixed bed reactors
Successive reaction.
Embodiment 1
0.8 g NaOH solids are dissolved in 16.6 g deionized waters, stirred.Then add the activation of 0.65 g sub-molten salts
Kaolin, in 70 DEG C of stirring in water bath 4 hours；Then 3.3 g white carbons and 0.3 g Beta molecular sieve seeds are slowly added respectively
Enter above-mentioned solution, stir 30 minutes；Mol ratio in terms of oxide is：40SiO2:Al2O3:10Na2O:660H2O.Will be above-mentioned mixed
Compound is incorporated with the stainless steel cauldron of polytetrafluoroethyllining lining, static crystallization 18 hours under the conditions of 140 DEG C.After cooling,
Solid product is filtered, washing, 120 DEG C of drying 12 hours, you can acquisition Beta molecular screen primary powders.By powder x-ray diffraction
After analysis, determine that BEA type molecular sieves that product is pure phase and relative crystallinity are 110%, the BET specific surface area of the product is 666
m2/g。
This Beta molecular sieve is used in the reaction of acetic acid and ethanol synthesizing ethyl acetate, reacted in fixed bed reactors
Successive reaction.
Embodiment 2
It is same as Example 1, only it is that silicon source white carbon is replaced with into Ludox (SiO2Content is 30 wt%), keep feed molar
Than for 40SiO2:Al2O3:10Na2O:660H2O.After powder x-ray diffraction analysis, the BEA types point that product is pure phase are determined
Son sieves and relative crystallinity is 102%, and the BET specific surface area of the product is 605 m2/g。
This Beta molecular sieve is used in the reaction of acetic acid and ethanol synthesizing ethyl acetate, reacted in fixed bed reactors
Successive reaction.
Embodiment 3
It is same as Example 1, only it is that water silicon ratio is changed to 20 (i.e. amount of water is changed into 20.2 g), the mol ratio in terms of oxide
For：40SiO2:Al2O3:10Na2O:800H2O.140 DEG C of static crystallizations 18 hours.After powder x-ray diffraction analysis, it is determined that
Product is the BEA types molecular sieve of pure phase and relative crystallinity is 105%, and the BET specific surface area of the product is 625 m2/g。
This Beta molecular sieve is used in the reaction of acetic acid and ethanol synthesizing ethyl acetate, reacted in fixed bed reactors
Successive reaction.
Embodiment 4
It is same as Example 1, only it is that crystallization temperature is changed to 120 DEG C, static crystallization 72 hours.By powder x-ray diffraction point
After analysis, determine that BEA type molecular sieves that product is pure phase and relative crystallinity are 118%, the BET specific surface area of the product is 680
m2/g。
This Beta molecular sieve is used in the reaction of acetic acid and ethanol synthesizing ethyl acetate, reacted in fixed bed reactors
Successive reaction.
Embodiment 5
It is same as Example 1, only it is that NaOH amount is reduced into by 0.3 g, i.e. material molar ratio is 40SiO2:Al2O3:8Na2O:
660H2O.After powder x-ray diffraction analysis, determine that BEA type molecular sieves that product is pure phase and relative crystallinity are 108%,
The BET specific surface area of the product is 656 m2/g。
This Beta molecular sieve is used in the reaction of acetic acid and ethanol synthesizing ethyl acetate, reacted in fixed bed reactors
Successive reaction.
Embodiment 6
It is same as Example 1, only it is that silicon source white carbon is replaced with into waterglass (SiO2Content is 28 wt%), keep feed molar
Than for 40SiO2:Al2O3:10Na2O:660H2O.After powder x-ray diffraction analysis, the BEA types point that product is pure phase are determined
Son sieves and relative crystallinity is 95%, and the BET specific surface area of the product is 620m2/g。
This Beta molecular sieve is used in the reaction of acetic acid and ethanol synthesizing ethyl acetate, reacted in fixed bed reactors
Successive reaction.
The Beta molecular sieves synthesized in embodiment 1 ~ 6 are applied to the esterification of acetic acid and ethanol, and reaction product is used
SHIMADZU GC-2014 gas chromatographs are analyzed, chromatographic column model Inertcap wax.Analysis result is shown in Table 1.
The acetic acid conversion and ethyl acetate of the comparative example of table 1 and each embodiment selectivity
As seen from the above table, compared with commercially available Beta molecular sieves, esterification of the Beta molecules to vinyl alcohol synthesized by the present invention
Reaction is with higher acetic acid conversion and ethyl acetate selectivity.Therefore, the Beta molecular sieves synthesized by the present invention have more
Excellent catalysis acetic acid and ethanol esterification performance.
Above-mentioned several embodiments are only several cases of the present invention, not do any formal limit to the present invention
System, although the present invention discloses preferable reaction condition as above, but the present invention is not limited to, it is any to be familiar with this specialty
Technical staff, without departing from the scope of the present invention, when the technology contents using the disclosure above make it is a little
Change or be modified to the equivalence enforcement case of equivalent variations.But every content without departing from technical solution of the present invention, according to this
Any simple modification, equivalent change and modification that the technical spirit of invention is made to above case study on implementation, belongs to the technology of the present invention
In aspects.
Claims (8)
- A kind of 1. preparation method of step hole Beta molecular sieves, it is characterised in that：The kaolin or rectorite activated with sub-molten salt For whole silicon sources and part silicon source, under conditions of any organic formwork agent is not added, have by step hydrothermal crystallizing synthesis The compound step hole Beta molecular sieves of macropore-micropore.
- A kind of 2. preparation method of step hole Beta molecular sieves as claimed in claim 1, it is characterised in that：By sodium hydroxide, The kaolin or rectorite of sub-molten salt activation, silicon source, crystal seed and deionized water are supplemented according to SiO2:Al2O3:Na2O:H2O=1: 0.01~0.05:0.2~0.35:8 ~ 20 molar ratio is well mixed, and Beta molecules are then obtained after aging, hydrothermal crystallizing Sieve.
- A kind of 3. preparation method of step hole Beta molecular sieves as claimed in claim 1 or 2, it is characterised in that：Described Asia Fused salt activates kaolin or the preparation method of rectorite is：By kaolin or rectorite with sodium hydroxide solution according to 1:2~1:20 Mass ratio be well mixed, then dried at 100 DEG C ~ 300 DEG C, products therefrom be activate after clay mineral；Wherein, It by sodium hydrate solid and water according to mass ratio is 1 that the sodium hydroxide solution, which is,:1~1:10 mix.
- A kind of 4. preparation method of step hole Beta molecular sieves as claimed in claim 2, it is characterised in that：Described crystal seed choosing With SiO commodity production or that laboratory synthesizes2/Al2O3Mol ratio is 15 ~ 30:1 Beta molecular sieves, quality is added to close The 1 ~ 10% of architectonical silicon source quality.
- A kind of 5. preparation method of step hole Beta molecular sieves as claimed in claim 2, it is characterised in that：Described supplement silicon Source is the one or more in white carbon, Ludox or waterglass.
- 6. step hole Beta molecular sieves made from preparation method as claimed in claim 1 or 2, it is characterised in that：Synthesized Beta molecular sieves are the compound step Porous materials of macropore-micropore of high-crystallinity, and its relative crystallinity is 80 ~ 120%, compares surface Product is 600 ~ 700 m2/g。
- A kind of 7. application of step hole as claimed in claim 6 Beta molecular sieves, it is characterised in that：For being catalyzed acetic acid and second In the reaction of alcohol synthesizing ethyl acetate.
- 8. application according to claim 7, it is characterised in that：Using fixed bed reactors successive reaction, acetic acid and ethanol The reaction temperature of synthesizing ethyl acetate is 100 ~ 150 DEG C, and reaction pressure is 0.08 ~ 0.2MPa, and the mol ratio of acetic acid and ethanol is 1:0.8~1:3, weight (hourly) space velocity (WHSV) is 0.8 ~ 2.0h-1。
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| US10287172B2 (en) * | 2014-11-19 | 2019-05-14 | China University Of Petroleum-Beijing | Preparation method for beta zeolite |
| CN112591765A (en) * | 2021-02-05 | 2021-04-02 | 福州大学 | Neutral polymer guiding step hole Beta molecular sieve and green preparation method thereof |
| CN113582197A (en) * | 2021-08-31 | 2021-11-02 | 青岛大学 | MOR molecular sieve with high silica-alumina ratio and preparation method thereof |
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| CN105384628A (en) * | 2015-11-17 | 2016-03-09 | 华东师范大学 | Preparation method of ester ether compound and catalyst applied to method |
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| CN109678177A (en) * | 2019-01-06 | 2019-04-26 | 福州大学 | A kind of preparation method of high silica alumina ratio step hole Beta molecular sieve |
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| CN112591765B (en) * | 2021-02-05 | 2021-07-09 | 福州大学 | Neutral polymer guiding step hole Beta molecular sieve and green preparation method thereof |
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