CN109734103A - Synthesize the method with the SAPO-34 molecular sieve of multi-stage artery structure - Google Patents
Synthesize the method with the SAPO-34 molecular sieve of multi-stage artery structure Download PDFInfo
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Abstract
The present invention relates to the synthesis field of molecular sieve, the method for specifically a kind of SAPO-34 molecular sieve of the synthesis with multi-stage artery structure.Using super dense gel rubber system, and crystal seed glue revulsive crystallization is added, the SAPO-34 molecular sieve of multi-stage porous is synthesized without adding mesoporous template, it is short between low in cost, easy to operate, reaction.The multi-stage porous SAPO-34 molecular sieve of preparation has many advantages, such as that mass transfer rate is fast, gas absorption amount is high and is not easy carbon distribution compared with conventional microporous SAPO-34, catalysis, absorption and in terms of there is critically important practical value.
Description
Technical field
The present invention relates to the synthesis field of molecular sieve, specifically a kind of synthesis has SAPO-34 points of multi-stage artery structure
The method of son sieve.
Background technique
SAPO-34 is the zeolite with CHA topological structure, the 3 D pore canal body with octatomic ring (0.38nm*0.38nm)
System and lower skeletal density, SAPO-34 type molecular sieve is with its unique cellular structure and selects the feature of type selectivity in methanol
Preparing low carbon hydrocarbons and gas separation etc. have broad application prospects.
SAPO-34 belongs to pore zeolite, and smaller hole road is conducive to the progress of shape selective catalysis, but is related to macromolecular ginseng some
With react, relatively small duct is but unfavorable for reactant molecule and is diffused into the catalytic active center in micropore,
The macromolecular for being unfavorable for generating is diffused out from reaction center, to will lead to the generation of carbon deposit, affects zeolite catalysis performance
And service life.On the other hand, the narrow duct of SAPO-34 molecular sieve makes gas molecule diffusion rate slower, is carrying out gas
When body absorption and separation, gas absorption equilibration time will increase, reduce separating effect and production efficiency.Therefore, synthesis contains Jie
The zeolitic material of hole cellular structure becomes a research due to that can improve the diffusion of material and improve catalyst activity
Hot spot.
Preparation multi-orifice zeolite material mainly has the methods of zeolite skeleton removing atom, template agent method.Wherein zeolite skeleton
Middle abjection atom refers to that this sloughs the silicon atom or aluminium atom in share price using vapor, acid etching, alkaline etching etc..This method is suitable
It is wide with property, but be largely lost using the zeolite micropore of the post-processings such as vapor soda acid, crystallinity decline, skeleton defect increases.
Referred to using mesoporous template method porous zeotile and carbon black, active carbon or surface-active are added in zeolite synthesis process
The removing of mesoporous template can be obtained by porous zeotile after zeolite synthesis by the templates such as agent, polymer.But it uses
Mesoporous template agent method preparation then can not really realize industrialized production due to high costs.
Summary of the invention
The present invention then can not really realize industrialization due to high costs to solve to prepare using mesoporous template agent method
The problem of production, provides a kind of method of SAPO-34 molecular sieve of the synthesis with multi-stage artery structure.
The present invention is achieved by the following technical solutions: a kind of synthesis has the SAPO-34 molecule of multi-stage artery structure
The method of sieve, comprising the following steps:
1) preparation of crystal seed glue
(1) silicon source is added into distilled water and is stirred, wait hydrolyze be added completely into tetraethyl ammonium hydroxide solution stirring, then plus
Enter phosphoric acid solution, continue to stir, be eventually adding silica solution and stir to form the first gel, for use；
(2) above-mentioned the first prepared gel is transferred in autoclave, heating is reacted, cooling in 150 DEG C of reaction 2h
To room temperature, the crystal seed glue of SAPO-34 is obtained；
2) preparation of super dense gel
(1) silicon source is added into distilled water and is stirred, wait hydrolyze be added completely into tetraethyl ammonium hydroxide solution stirring, then plus
Enter phosphoric acid solution, continue to stir, be eventually adding silica solution and stir to form the second gel, for use；
(2) crystal seed glue is added in the second gel prepared, stirring forms mixture；
(3) mixture 1 ~ 4h of heating stirring under 70 DEG C ~ 100 DEG C of heating temperature can be obtained super dense as the solvent evaporates
Gel；
3) Crystallization of Zeolite
(1) super dense gel is placed in autoclave, heating is reacted, and reaction temperature is 120-150 DEG C, and the reaction time is
12~36h；
(2) after reacting after product washing, filtering, drying, SAPO-34 molecular sieve is can be obtained in roasting.
As the further improvement of technical solution of the present invention, silicon source (in terms of aluminium oxide), distillation in the step 1)-(1)
Water, tetraethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid are (with H3PO4Meter) and silica solution (with SiO2Meter) molar ratio be 1:50 ~
100:2.0 ~ 2.8:1.8 ~ 2.2:0.1 ~ 0.4.
As the further improvement of technical solution of the present invention, it is described 2)-(1) in silicon source (in terms of aluminium oxide), distilled water, four
Ethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid are (with H3PO4Meter) and silica solution (with SiO2Meter) molar ratio be 1:0 ~ 20:1.5 ~
2.2:1.8 ~ 2.2:0.1 ~ 0.4.
As the further improvement of technical solution of the present invention, the step 1)-(1) neutralizes 2)-(1) in silicon source be isopropyl
Aluminium alcoholates, diaspore, boehmite or aluminium oxide.
As the further improvement of technical solution of the present invention, the process of the roasting are as follows: with the heating rate liter of 5 DEG C/min
To 200 DEG C of holding 3h, 550 DEG C then are continuously heating to phase same rate, keeps the temperature 5 hours, finally with the cooling of 10 DEG C/min rate
To room temperature.
As the further improvement of technical solution of the present invention, the quality of the second gel and crystal seed glue in the step 2-(2)
Than for 1:0.1 ~ 0.5.
As the further improvement of technical solution of the present invention, in the step 2-(3) rate of heating stirring be 30rpm ~
100rpm。
The present invention uses super dense gel rubber system, and crystal seed glue inducing molecule sieve crystallization is added, and has synthesized the SAPO- of multi-stage porous
34 molecular sieves.SAPO-34 molecular sieve using this method synthesis has biggish mesoporous Kong Rong and specific surface area.And the present invention
Mesoporous template is not added, it is short between low in cost, easy to operate, reaction, there is biggish industrial applicability prospect.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the comparison of the XRD diffraction pattern and SAPO-34 standard diagram of embodiment 1.Its peak shape fits like a glove, it was demonstrated that real
Applying example 1 is SAPO-34.
Fig. 2 is the 77K nitrogen adsorption isotherm figure of embodiment 1.The adsorption curve belongs to IV type thermoisopleth, inhales in low-pressure area
Attached amount is higher, hysteresis loop occurs in 0.5P0-1.0P0, shows to include a large amount of micropores and slit-type in synthesized zeolitic material
It is mesoporous, it is a kind of multilevel hole material.
Fig. 3 is the graph of pore diameter distribution of embodiment 1.As can be seen that the aperture of synthesized zeolitic material is main from this figure
5.5 and 50-100 are distributed in, are a kind of multilevel hole materials.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Technical solution of the present invention is described in detail with reference to the accompanying drawing.
A method of synthesizing the SAPO-34 molecular sieve with multi-stage artery structure, comprising the following steps:
1) preparation of crystal seed glue
(1) silicon source is added into distilled water and is stirred, wait hydrolyze be added completely into tetraethyl ammonium hydroxide solution stirring, then plus
Enter phosphoric acid solution, continue to stir, be eventually adding silica solution and stir to form the first gel, for use；
(2) above-mentioned the first prepared gel is transferred in autoclave, heating is reacted, cooling in 150 DEG C of reaction 2h
To room temperature, the crystal seed glue of SAPO-34 is obtained；
2) preparation of super dense gel
(1) silicon source is added into distilled water and is stirred, wait hydrolyze be added completely into tetraethyl ammonium hydroxide solution stirring, then plus
Enter phosphoric acid solution, continue to stir, be eventually adding silica solution and stir to form the second gel, for use；
(2) crystal seed glue is added in the second gel prepared, stirring forms mixture；
(3) mixture 1 ~ 4h of heating stirring under 70 DEG C ~ 100 DEG C of heating temperature can be obtained super dense as the solvent evaporates
Gel；In the step, heating temperature is preferably 80 ~ 90 DEG C, and the preferred heating stirring time is 2 ~ 3h；
3) Crystallization of Zeolite
(1) super dense gel is placed in autoclave, heating is reacted, and reaction temperature is 120-150 DEG C, and the reaction time is
12~36h；In this step, reaction temperature is preferably 130-140 DEG C, and the preferred reaction time is 20-24 h；
(2) after reacting after product washing, filtering, drying, SAPO-34 molecular sieve is can be obtained in roasting.
Further, silicon source (in terms of aluminium oxide) in the step 1)-(1), distilled water, tetraethyl ammonium hydroxide (with
TEAOH meter), phosphoric acid is (with H3PO4Meter) and silica solution (with SiO2Meter) molar ratio be 1:50 ~ 100:2.0 ~ 2.8:1.8 ~ 2.2:
0.1~0.4.Preferably, silicon source (in terms of aluminium oxide), distilled water, tetraethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid are (with H3PO4
Meter) and silica solution (with SiO2Meter) molar ratio be 1:70:2.5:2.0:0.3.
As the further improvement of technical solution of the present invention, it is described 2)-(1) in silicon source (in terms of aluminium oxide), distilled water, four
Ethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid are (with H3PO4Meter) and silica solution (with SiO2Meter) molar ratio be 1:0 ~ 20:1.5 ~
2.2:1.8 ~ 2.2:0.1 ~ 0.4.Preferably, silicon source (in terms of aluminium oxide), distilled water, tetraethyl ammonium hydroxide (in terms of TEAOH),
Phosphoric acid is (with H3PO4Meter) and silica solution (with SiO2Meter) molar ratio be 1:5:2.0:2.0:0.3.
As the further improvement of technical solution of the present invention, the step 1)-(1) neutralizes 2)-(1) in silicon source be isopropyl
Aluminium alcoholates, diaspore, boehmite or aluminium oxide.
As the further improvement of technical solution of the present invention, the process of the roasting are as follows: with the heating rate liter of 5 DEG C/min
To 200 DEG C of holding 3h, 550 DEG C then are continuously heating to phase same rate, keeps the temperature 5 hours, finally with the cooling of 10 DEG C/min rate
To room temperature.
As the further improvement of technical solution of the present invention, the quality of the second gel and crystal seed glue in the step 2-(2)
Than for 1:0.1 ~ 0.5.It is preferred that 1:0.2.
As the further improvement of technical solution of the present invention, in the step 2-(3) rate of heating stirring be 30rpm ~
100rpm, preferably 60rpm.
Embodiment 1
A method of synthesizing the SAPO-34 molecular sieve with multi-stage artery structure, comprising the following steps:
1) preparation of crystal seed glue
(1) 2.04g aluminium isopropoxide is slowly added in 6.30ml distilled water and is stirred, be added completely into 7.21ml concentration wait hydrolyze and be
The tetraethyl ammonium hydroxide solution (density 1.02g/ml) of 25wt% stirs 0.5h.Being subsequently added into 0.68ml mass fraction is 85wt%
Phosphoric acid solution (1.69 g/ml of density), continue stir 0.5h.It is (close to be eventually adding the silica solution that 0.17ml concentration is 40wt%
Spend 1.3 g/ml) and 1 hour the first gel of formation is stirred, for use.Silicon source (in terms of aluminium oxide), distillation in the step 1)-(1)
Water, tetraethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid are (with H3PO4Meter) and silica solution (with SiO2Meter) molar ratio be 1:70:
2.5:2:0.3.
(2) above-mentioned the first prepared gel being transferred in autoclave, heating is reacted, in 150 DEG C of reaction 2h,
It is cooled to room temperature, obtains the crystal seed glue of SAPO-34；
2) preparation of super dense gel
It (1) is the tetraethyl ammonium hydroxide of 25wt% by water and 5.76ml concentration that 2.04g aluminium isopropoxide is slowly added to 0.45ml
Solution stirs 0.5h.It is subsequently added into the phosphoric acid solution that 0.68ml mass fraction is 85wt%, continues to stir 0.5h.It is eventually adding
0.24ml concentration is 1 hour the second gel of formation of the silica solution of 40wt% and stirring, for use.It is described 2)-(1) in silicon source (with oxygen
Change aluminium meter), distilled water, tetraethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid is (with H3PO4Meter) and silica solution (with SiO2Meter) rub
You are than being 1:5:2.0:2.0:0.3.
(2) 1.6g crystal seed glue is added in the second gel prepared, stirring 0.5h forms mixture；
(3) super dense gel can be obtained as the solvent evaporates in mixture heating stirring 3h under 90 DEG C of heating temperature；
3) Crystallization of Zeolite
(1) super dense gel is placed in autoclave, heating is reacted, and reaction temperature is 140 DEG C, reaction time 20h；
(2) it will be roasted after product washing, filtering, drying after reaction, roasting process is with the heating rate of 5 DEG C/min
200 DEG C of holding 3h are risen to, are then continuously heating to 550 DEG C with phase same rate, keep the temperature 5 hours, finally with 10 DEG C/min rate drop
It warms to room temperature, the SAPO-34 molecular sieve with multi-stage artery structure is made.
Following table is the specific surface area and Kong Rong of embodiment 1.
| BET specific surface area | Langmuir specific surface area | Micropore volume | Mesoporous Kong Rong | External surface area |
| 684.89m2/g | 941.15m2/g | 0.31cm3/g | 0.10cm3/g | 49.53 m2/g |
Embodiment 2
A method of synthesizing the SAPO-34 molecular sieve with multi-stage artery structure, comprising the following steps:
1) preparation of crystal seed glue
(1) 0.51g aluminium oxide is slowly added in 6.30ml distilled water and is stirred, be added completely into 5.05ml concentration wait hydrolyze and be
The tetraethyl ammonium hydroxide solution (density 1.04g/ml) of 35wt% stirs 0.5h.Being subsequently added into 0.68ml mass fraction is 85wt%
Phosphoric acid solution (density 1.69g/ml), continue stir 0.5h.It is eventually adding the silica solution (density that 0.41ml concentration is 20wt%
1.1g/ml) and 1 hour the first gel of formation is stirred, for use.Silicon source (in terms of aluminium oxide) in the step 1)-(1), distilled water,
Tetraethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid are (with H3PO4Meter) and silica solution (with SiO2Meter) molar ratio be 1:70:2.5:
2:0.3.
(2) above-mentioned the first prepared gel being transferred in autoclave, heating is reacted, in 150 DEG C of reaction 2h,
It is cooled to room temperature, obtains the crystal seed glue of SAPO-34；
2) preparation of super dense gel
(1) water and the 5.76ml concentration for 0.51g aluminium oxide being slowly added to 0.45ml are molten for the tetraethyl ammonium hydroxide of 25wt%
Liquid stirs 0.5h.It is subsequently added into the phosphoric acid solution that 0.68ml mass fraction is 85wt%, continues to stir 0.5h.It is eventually adding
0.45ml concentration is 1 hour the second gel of formation of the silica solution of 20wt% and stirring, for use.It is described 2)-(1) in silicon source (with oxygen
Change aluminium meter), distilled water, tetraethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid is (with H3PO4Meter) and silica solution (with SiO2Meter) rub
You are than being 1:5:2.0:2.0:0.3.
(2) 1.6g crystal seed glue is added in the second gel prepared, stirring 0.5h forms mixture；
(3) super dense gel can be obtained as the solvent evaporates in mixture heating stirring 3h under 90 DEG C of heating temperature；
3) Crystallization of Zeolite
(1) super dense gel is placed in autoclave, heating is reacted, and reaction temperature is 140 DEG C, reaction time 20h；
(2) it will be roasted after product washing, filtering, drying after reaction, roasting process is with the heating rate of 5 DEG C/min
200 DEG C of holding 3h are risen to, are then continuously heating to 550 DEG C with phase same rate, keep the temperature 5 hours, finally with 10 DEG C/min rate drop
It warms to room temperature, the SAPO-34 molecular sieve with multi-stage artery structure is made.
Embodiment 3
A method of synthesizing the SAPO-34 molecular sieve with multi-stage artery structure, comprising the following steps:
1) preparation of crystal seed glue
(1) 2.04g aluminium isopropoxide is slowly added in 6.30ml distilled water and is stirred, be added completely into 7.21ml concentration wait hydrolyze and be
The tetraethyl ammonium hydroxide solution (density 1.02g/ml) of 25wt% stirs 0.5h.Being subsequently added into 0.68ml mass fraction is 85wt%
Phosphoric acid solution (density 1.69g/ml), continue stir 0.5h.It is eventually adding the silica solution (density that 0.24ml concentration is 40wt%
1.3g/ml) and 1 hour the first gel of formation is stirred, for use.Silicon source (in terms of aluminium oxide) in the step 1)-(1), distilled water,
Tetraethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid are (with H3PO4Meter) and silica solution (with SiO2Meter) molar ratio be 1:70:2.5:
2:0.3.
(2) above-mentioned the first prepared gel being transferred in autoclave, heating is reacted, in 150 DEG C of reaction 2h,
It is cooled to room temperature, obtains the crystal seed glue of SAPO-34；
2) preparation of super dense gel
It (1) is the tetraethyl ammonium hydroxide of 25wt% by water and 5.76ml concentration that 2.04g aluminium isopropoxide is slowly added to 4.5ml
Solution stirs 0.5h.It is subsequently added into the phosphoric acid solution that 0.68ml mass fraction is 85wt%, continues to stir 0.5h.It is eventually adding
0.17ml concentration is 1 hour the second gel of formation of the silica solution of 40wt% and stirring, for use.It is described 2)-(1) in silicon source (with oxygen
Change aluminium meter), distilled water, tetraethyl ammonium hydroxide (in terms of TEAOH), phosphoric acid is (with H3PO4Meter) and silica solution (with SiO2Meter) rub
You are than being 1:50:2.0:2.0:0.3.
(2) 1.6g crystal seed glue is added in the second gel prepared, stirring 0.5h forms mixture；
(3) super dense gel can be obtained as the solvent evaporates in mixture heating stirring 3h under 90 DEG C of heating temperature；
3) Crystallization of Zeolite
(1) super dense gel is placed in autoclave, heating is reacted, and reaction temperature is 150 DEG C, reaction time 36h；
(2) it after reacting after product washing, filtering, drying, is roasted, roasting process is with the heating rate liter of 5 DEG C/min
To 200 DEG C of holding 3h, 550 DEG C then are continuously heating to phase same rate, 5h is kept the temperature, room is finally cooled to 10 DEG C/min rate
The SAPO-34 molecular sieve with multi-stage artery structure can be obtained in temperature.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (7)
1. a kind of method that synthesis has the SAPO-34 molecular sieve of multi-stage artery structure, which comprises the following steps:
1) preparation of crystal seed glue
(1) silicon source is added into distilled water and is stirred, wait hydrolyze be added completely into tetraethyl ammonium hydroxide solution stirring, then plus
Enter phosphoric acid solution, continue to stir, be eventually adding silica solution and stir to form the first gel, for use；
(2) above-mentioned the first prepared gel is transferred in autoclave, heating is reacted, cooling in 150 DEG C of reaction 2h
To room temperature, the crystal seed glue of SAPO-34 is obtained；
2) preparation of super dense gel
(1) silicon source is added into distilled water and is stirred, wait hydrolyze be added completely into tetraethyl ammonium hydroxide solution stirring, then plus
Enter phosphoric acid solution, continue to stir, be eventually adding silica solution and stir to form the second gel, for use；
(2) crystal seed glue is added in the second gel prepared, stirring forms mixture；
(3) mixture 1 ~ 4h of heating stirring under 70 DEG C ~ 100 DEG C of heating temperature can be obtained super dense as the solvent evaporates
Gel；
3) Crystallization of Zeolite
(1) super dense gel is placed in autoclave, heating is reacted, and reaction temperature is 120-150 DEG C, and the reaction time is
12~36h；
(2) after reacting after product washing, filtering, drying, SAPO-34 molecular sieve is can be obtained in roasting.
2. the method that a kind of synthesis according to claim 1 has the SAPO-34 molecular sieve of multi-stage artery structure, feature
Be, silicon source in the step 1)-(1), distilled water, tetraethyl ammonium hydroxide, phosphoric acid and silica solution molar ratio be 1:50 ~
100:2.0 ~ 2.8:1.8 ~ 2.2:0.1 ~ 0.4.
3. the method that a kind of synthesis according to claim 1 has the SAPO-34 molecular sieve of multi-stage artery structure, feature
Be, it is described 2)-(1) in silicon source, distilled water, tetraethyl ammonium hydroxide, phosphoric acid and silica solution molar ratio be 1:0 ~ 20:1.5 ~
2.2:1.8 ~ 2.2:0.1 ~ 0.4.
4. the method that a kind of synthesis according to claim 2 or 3 has the SAPO-34 molecular sieve of multi-stage artery structure,
Be characterized in that, the step 1)-(1) neutralizes 2)-(1) in silicon source be aluminium isopropoxide, diaspore, boehmite or oxidation
Aluminium.
5. the method that a kind of synthesis according to claim 1 or 2 or 3 has the SAPO-34 molecular sieve of multi-stage artery structure,
It is characterized in that, the process of the roasting are as follows: 200 DEG C of holding 3h are risen to the heating rate of 5 DEG C/min, then with phase same rate
550 DEG C are continuously heating to, 5 hours is kept the temperature, room temperature is finally cooled to 10 DEG C/min rate.
6. the method that a kind of synthesis according to claim 1 or 2 or 3 has the SAPO-34 molecular sieve of multi-stage artery structure,
It is characterized in that, the mass ratio of the second gel and crystal seed glue is 1:0.1 ~ 0.5 in the step 2-(2).
7. the method that a kind of synthesis according to claim 1 has the SAPO-34 molecular sieve of multi-stage artery structure, feature
It is, the rate of heating stirring is 30rpm ~ 100rpm in the step 2-(3).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115193408A (en) * | 2022-07-15 | 2022-10-18 | 盐城工学院 | Ag-SAPO-34@ Cu-BTC composite material and preparation and application methods thereof |
| CN115364894A (en) * | 2022-08-25 | 2022-11-22 | 太原理工大学 | Preparation method of high-selectivity catalyst for preparing olefin from methanol |
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| CN101555020A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Synthesis method of SAPO molecular sieve |
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2019
- 2019-03-12 CN CN201910184598.7A patent/CN109734103A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555020A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Synthesis method of SAPO molecular sieve |
Non-Patent Citations (1)
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| CHANGSHENG ZHANG等: ""An efficient, rapid, and non-centrifugation synthesis of nanosized zeolites by accelerating the nucleation rate"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115193408A (en) * | 2022-07-15 | 2022-10-18 | 盐城工学院 | Ag-SAPO-34@ Cu-BTC composite material and preparation and application methods thereof |
| CN115193408B (en) * | 2022-07-15 | 2023-05-05 | 盐城工学院 | Ag-SAPO-34@Cu-BTC composite material and preparation and application methods thereof |
| CN115364894A (en) * | 2022-08-25 | 2022-11-22 | 太原理工大学 | Preparation method of high-selectivity catalyst for preparing olefin from methanol |
| CN115364894B (en) * | 2022-08-25 | 2023-06-06 | 太原理工大学 | Preparation method of high-selectivity catalyst for preparing olefin from methanol |
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