CN108033463A - The method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under no organic amine system - Google Patents
The method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under no organic amine system Download PDFInfo
- Publication number
- CN108033463A CN108033463A CN201711494447.9A CN201711494447A CN108033463A CN 108033463 A CN108033463 A CN 108033463A CN 201711494447 A CN201711494447 A CN 201711494447A CN 108033463 A CN108033463 A CN 108033463A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- crystallization
- zsm
- organic amine
- silicon source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a kind of without the method that 5 molecular sieve of fine grain ZSM-5 is efficiently synthesized under organic amine system, this method uses silicon source, silicon source, alkali source, Longer-chain surfactants as raw material, prepare the molecular sieve gel without organic amine, degree of adoption heating crystallization growth, 5 molecular sieve of aggregated form fine grain ZSM-5 is obtained, its particle diameter is less than 5 molecular sieves of ZSM of traditional Template-free method method synthesis.The method of the present invention substitutes the use of organic amine template by adding Longer-chain surfactants, reduce water consumption at the same time, the water silicon ratio that feeds intake is less than 15, combine solid phase and the synthesis advantage of liquid phase crystallization, molecular sieve yield is high, waste water is few, and production cost is low, effectively overcomes a series of problems such as high cost and environmental pollution that prior synthesizing method is largely brought using organic amine template.
Description
Technical field：
The invention belongs to molecular sieve preparation field, and in particular to it is a kind of without efficiently prepared under organic amine system fine grain ZSM-5-
The method of 5 molecular sieves.
Background technology：
ZSM-5 molecular sieve determines its hydrothermal stability and good with its unique three-dimensional open-framework and acid strength distribution
Shape selectivity, especially the aromatisation of hydro carbons, isomerization, alkylation and aromatic disproportion etc. reaction in show brilliance performance,
The purpose of improving octane number, reduction content of olefin in gasoline, producing more propylene can be reached by being used as catalytic cracking reaction.Together
When ZSM-5 molecular sieve be also widely used for the every field such as adsorbing separation, ion exchange and environmental protection.
Mobil Corporation (R.J.Argauer, G.R.Landolt.US3702886,1972) report use first in 1972 has
Machine template success synthetic ZSM-5 zeolite.Follow-up many scholars also report organic formwork agent method synthetic ZSM-5 zeolite molecule
Sieve.The use of organic formwork agent can bring many problems, for example improve synthesis cost, and template removes not exclusively can plugging hole
Road, so as to influence the activity of catalyst.The decomposition of template can bring the environmental problems such as pollution to air and water.
Huang et al. uses high temperature to be nucleated low temperature crystallized two-step method under the addition of Template-free method using Ludox as silicon source
ZSM-5 molecular sieve cluster body [HuangXL, etal., Chin.J.Catal., 2011,11 of larger crystal particle diameter are synthesized:
1702-1710], there are the shortcomings that water silicon is bigger, and synthesis of molecular sieve particle diameter is larger for this method；
Patent CN101643219A and CN201610256314.7 are required to introduce in the synthesis process and are closed using organic amine
Into MFI crystal seeds, can not avoid the use of organic amine in the synthesis process, and the molecular sieve synthesized is uneven there are pattern, it is brilliant
The shortcomings of particle size is larger and wider distribution, and crystallinity is less high.
Patent CN101643219A, CN102642847B and CN201610256314.7 are in building-up process liquid water usage amount
It is larger, cause the solid-to-liquid ratio in building-up process relatively low, the yield of molecular sieve is low, improves the cost of synthesis to a certain extent.
In short, the above method and other related similar approach can efficiently reduce the use of organic ammonium, but still
Inevitably use organic amine template, simultaneously synthesizing obtained ZSM-5 molecular sieve is larger there are particle diameter, pattern inequality
It is even, at the same molecular sieve yield it is relatively low the problems such as, this just greatly limit the industrial applications of such synthetic method.
The content of the invention
It is a kind of without efficient preparation ZSM-5 under organic amine system the purpose of the present invention is overcoming the deficiencies of the prior art and provide
The method of molecular sieve, this method substitute the use of organic amine by Longer-chain surfactants, while reduce water silicon ratio, combine solid
Mutually with the synthesis advantage of liquid phase crystallization, molecular sieve yield is high, and waste water is few, and production cost is low, effectively overcomes prior synthesizing method big
Measure a series of problems such as the high cost brought using organic amine template and environmental pollution.
The technical solution of the present invention has been to provide a kind of without efficiently synthesizing small-grain ZSM-5 point under organic amine system
The method of son sieve, substitutes organic amine by adding Longer-chain surfactants, reduces water consumption, and the water silicon ratio that feeds intake is less than 15, with reference to
The synthesis advantage of solid phase crystallization and liquid phase crystallization, the reaction time is short, molecular sieve product high income.It is specific as follows：
It is a kind of as follows without the method that ZSM-5 molecular sieve with small crystal grains is efficiently synthesized under organic amine system, its specific preparation process：
(1) silicon source, alkali source, surfactant are dissolved in deionized water respectively, stirred evenly at room temperature.
(2) silicon source is added, is sufficiently stirred and is made into mixed glue solution, its total moles ratio of components is SiO2:Al2O3:Na2O:S:H2O
=1:(0.005-0.038):(0.03-0.12):(0.003-0.03):(3-15), wherein Na2O represents basicity, S represents long-chain
Class surfactant.
(3) mixed glue solution obtained in step (2) is fitted into stainless steel cauldron, is then divided to two sections at different temperatures
Dynamic crystallization, first segment crystallization temperature is 50~120 DEG C, and when crystallization 12~48 is small, second segment crystallization temperature is 120~180 DEG C,
When crystallization 12~72 is small；Filtered after reaction, washing, drying, roast to obtain ZSM-5 molecular sieve.
Wherein, the silicon source is silica gel, white carbon at least one；Source of aluminium is sodium metaaluminate, aluminum nitrate, isopropanol
At least one of aluminium, aluminum sulfate；The alkali is potassium hydroxide or sodium hydroxide；The surfactant is detergent alkylate
Sodium sulfonate (SDBS), sodium sulfate of polyethenoxy ether of fatty alcohol (AES) or methyl sodiosul foaliphatate (MES) are one or two kinds of
Mixing.
According to preparation method of the present invention, its preferred solution is characterized in that：
Processing step includes：
(1) silicon source, sodium hydroxide, surfactant are dissolved in deionized water, stirred evenly at room temperature.
(2) silicon source is added, is sufficiently stirred and is made into mixed glue solution, its total moles ratio of components is SiO2:Al2O3:Na2O:S:H2O
=1:(0.012-0.034):(0.05-0.085):(0.008-0.025):(4-10), wherein Na2O represents basicity, S represents length
Chain surfactant.
(3) mixed glue solution obtained in step (2) is fitted into stainless steel cauldron, 80-120 DEG C of crystallization 12-36h, 140
DEG C of -170 DEG C crystallization 24h-48h, filtered after reaction, washing, it is dry, roast to obtain ZSM-5 molecular sieve.
Compared with prior art, the present invention its innovative point and advantage are：
It is cheap and easy to get, dosage is few 1. the Longer-chain surfactants that the present invention uses, while instead of organic amine or contain
There is the use of organic amine nucleus liquid, it is relatively small to environment and body harm, reduce production cost.
2. the ZSM-5 molecules relative crystallinity of synthetic method synthesis provided by the invention is high, particle diameter is less than usually without template
The ZSM-5 molecular sieve of agent method synthesis, while there is certain reunion in molecular sieve, is easily isolated.
3. the present invention improves synthesis solid-to-liquid ratio, with reference to solid to a certain extent by the use of Longer-chain surfactants
The advantage of phase crystallization and liquid phase crystallization, improves the yield of molecular sieve.
4. segmentation crystallization method used by synthetic method provided by the invention, improves the utilization rate and product of reactant
Yield, reduces production cost.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of gained molecular sieve in the embodiment of the present invention 1.
Fig. 2 is the surface sweeping electromicroscopic photograph (SEM) of gained molecular sieve in the embodiment of the present invention 1.
Fig. 3 is X-ray diffraction (XRD) spectrogram of gained molecular sieve in the embodiment of the present invention 2.
Fig. 4 is the surface sweeping electromicroscopic photograph (SEM) of gained molecular sieve in the embodiment of the present invention 2.
Fig. 5 is X-ray diffraction (XRD) spectrogram of gained molecular sieve in comparative example of the present invention.
Fig. 6 is the surface sweeping electromicroscopic photograph (SEM) of gained molecular sieve in comparative example of the present invention.
Embodiment
The present invention is further described with comparative example by the following examples, but it is not thereby limiting the invention
Can practical range.For those skilled in the art, the record according to present specification can be completed without under organic amine system completely
ZSM-5 molecular sieve efficiently synthesizes.
Implementation column 1
Weigh 4.72g aluminium isopropoxides to be dissolved in 45.40g deionized waters, sequentially add 3.96g sodium hydroxides, stirring makes it
Dissolving；Weigh 1.58gSDBS to be dissolved in 38.96g deionized waters, add into above-mentioned solution, be sufficiently stirred to obtain silicon source mixed liquor.
59.27g white carbons are weighed, are added under stirring condition into silicon source mixed liquor, after being sufficiently mixed uniformly, are transferred to interior
In the reaction kettle of lining teflon, cool down after 80 DEG C of crystallization 24h, 180 DEG C of crystallization 24h, product is filtered, washs, is dry, roasting
Burn to obtain ZSM-5 molecular sieve.
Embodiment 2
Weigh 6.12g aluminium isopropoxides to be dissolved in 60g deionized waters, sequentially add 8.14g sodium hydroxides, stirring makes its molten
Solution；Weigh 3.45gAES to be dissolved in 48g deionized waters, add into above-mentioned solution, be sufficiently stirred to obtain silicon source mixed liquor.
71.12g white carbons are weighed, are added under stirring condition into silicon source mixed liquor, after being sufficiently mixed uniformly, are transferred to interior
In the reaction kettle of lining teflon, cool down after 100 DEG C of crystallization 36h, 170 DEG C of crystallization 34h, product is filtered, washing, it is dry,
Roast to obtain ZSM-5 molecular sieve.
Embodiment 3
Weigh 12.01g sodium metaaluminates to be dissolved in 168g deionized waters, sequentially add 10.53g sodium hydroxides, stirring makes it
Dissolving；Weigh 9.48gMES to be dissolved in 87g deionized waters, add into above-mentioned solution, be sufficiently stirred to obtain silicon source mixed liquor.
96.98g silica gel is weighed, is added under stirring condition into silicon source mixed liquor, after being sufficiently mixed uniformly, is transferred to liner
In the reaction kettle of polytetrafluoroethylene (PTFE), cool down after 120 DEG C of crystallization 24h, 150 DEG C of crystallization 20h, product is filtered, washs, is dry, roasting
Burn to obtain ZSM-5 molecular sieve.
Embodiment 4
Weigh 12.05g sodium metaaluminates to be dissolved in 157g deionized waters, sequentially add 10.81g sodium hydroxides, stirring makes it
Dissolving；Weigh 6.75gSDBS, 3.55gAES to be dissolved in 91g deionized waters, add into above-mentioned solution, be sufficiently stirred to obtain silicon source
Mixed liquor.
106.68g silica gel is weighed, is added under stirring condition into silicon source mixed liquor, after being sufficiently mixed uniformly, is transferred to interior
In the reaction kettle of lining teflon, cool down after 100 DEG C of crystallization 48h, 150 DEG C of crystallization 24h, product is filtered, washing, it is dry,
Roast to obtain ZSM-5 molecular sieve.
Embodiment 5
Weigh 9.55g sodium metaaluminates to be dissolved in 128g deionized waters, sequentially add 11.25g sodium hydroxides, stirring makes its molten
Solution；Weigh 2.16gSDBS, 4.88gAES be dissolved in 115g deionized waters, add into above-mentioned solution, be sufficiently stirred silicon source is mixed
Close liquid.
118.67g silica gel is weighed, is added under stirring condition into silicon source mixed liquor, after being sufficiently mixed uniformly, is transferred to interior
In the reaction kettle of lining teflon, cool down after 120 DEG C of crystallization 24h, 160 DEG C of crystallization 36h, product is filtered, washing, it is dry,
Roast to obtain ZSM-5 molecular sieve.
Embodiment 6
Weigh 21.3g aluminum sulfate to be dissolved in 142g deionized waters, sequentially add 14.4g sodium hydroxides, stir to dissolve；
Weigh 3.27gSLS, 1.05gAES to be dissolved in 82g deionized waters, add into above-mentioned solution, be sufficiently stirred to obtain silicon source mixed liquor.
62.75g white carbons are weighed, are added under stirring condition into silicon source mixed liquor, after being sufficiently mixed uniformly, are transferred to interior
In the reaction kettle of lining teflon, cool down after 80 DEG C of crystallization 36h, 170 DEG C of crystallization 36h, product is filtered, washs, is dry, roasting
Burn to obtain ZSM-5 molecular sieve.
Embodiment 7
Weigh 8.2g aluminium isopropoxides to be dissolved in 113.6g deionized waters, sequentially add 7.8g sodium hydroxides, stirring makes its molten
Solution；Weigh 2.6gSLS, 2.51gSDBS to be dissolved in 42.26g deionized waters, add into above-mentioned solution, be sufficiently stirred to obtain silicon source
Mixed liquor.
62.75g silica gel is weighed, is added under stirring condition into silicon source mixed liquor, after being sufficiently mixed uniformly, is transferred to liner
In the reaction kettle of polytetrafluoroethylene (PTFE), cool down after 120 DEG C of crystallization 24h, 150 DEG C of crystallization 36h, product is filtered, washs, is dry, roasting
Burn to obtain ZSM-5 molecular sieve.
The real embodiment of contrast：
Weigh 12g sodium metaaluminates to be dissolved in 186g deionized waters, sequentially add 10.83g sodium hydroxides, stirring makes its molten
Solution, is sufficiently stirred to obtain silicon source mixed liquor.
106.68g silica gel is weighed, is added under stirring condition into silicon source mixed liquor, it is brilliant to add 3.2g ZSM-5 molecular sieves
Kind, after being sufficiently mixed uniformly, it is transferred in the reaction kettle of inner liner polytetrafluoroethylene, cools down after 170 DEG C of crystallization 72h, product passes through
Filter, wash, be dry, roasting to obtain ZSM-5 molecular sieve.
Claims (3)
- It is 1. a kind of without the method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under organic amine system, it is characterised in that including following step Suddenly：(1) silicon source, alkali source, surfactant are dissolved in deionized water respectively, stirred evenly at room temperature；(2) silicon source is added, is sufficiently stirred and is made into mixed glue solution, its total moles ratio of components is SiO2:Al2O3:Na2O:S:H2O=1: (0.005-0.038):(0.03-0.12):(0.003-0.03):(3-15), wherein S are long-chain class surfactant；(3) mixed glue solution obtained in step (2) is fitted into stainless steel cauldron, is then divided to two sections of dynamics at different temperatures Crystallization, first segment crystallization temperature is 50~120 DEG C, and when crystallization 12~48 is small, second segment crystallization temperature is 120~180 DEG C, crystallization 12~72 it is small when；Filtered after reaction, washing, drying, roast to obtain ZSM-5 molecular sieve；Wherein, the silicon source is at least one of silica gel, white carbon；Source of aluminium is sodium metaaluminate, aluminum nitrate, isopropanol At least one of aluminium, aluminum sulfate；The alkali is potassium hydroxide or sodium hydroxide；The surfactant is detergent alkylate One or two kinds of mixing in sodium sulfonate, sodium sulfate of polyethenoxy ether of fatty alcohol and methyl sodiosul foaliphatate.
- 2. according to the preparation method described in claims 1, it is characterised in that：The mixed glue solution that the step (2) is made into Total total moles ratio of components is SiO2:Al2O3:Na2O:S:H2O=1:(0.012-0.034):(0.05-0.085):(0.008- 0.025):(4-10), wherein S are Longer-chain surfactants.
- 3. according to the preparation method described in claims 2, it is characterised in that include the following steps：(1) silicon source, sodium hydroxide, surfactant are dissolved in deionized water, stirred evenly at room temperature.(2) silicon source is added, is sufficiently stirred and is made into mixed glue solution；(3) mixed glue solution obtained in step (2) is fitted into stainless steel cauldron, 80-120 DEG C of crystallization 12-36h, 140 DEG C- 170 DEG C of crystallization 24h-48h, filtered after reaction, washing, drying, roast to obtain ZSM-5 molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711494447.9A CN108033463A (en) | 2017-12-31 | 2017-12-31 | The method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under no organic amine system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711494447.9A CN108033463A (en) | 2017-12-31 | 2017-12-31 | The method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under no organic amine system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108033463A true CN108033463A (en) | 2018-05-15 |
Family
ID=62099245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711494447.9A Pending CN108033463A (en) | 2017-12-31 | 2017-12-31 | The method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under no organic amine system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108033463A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179446A (en) * | 2018-09-28 | 2019-01-11 | 青岛大学 | A kind of hollow nano H-type ZSM-5 molecular sieve and preparation method thereof |
| CN109553114A (en) * | 2019-01-16 | 2019-04-02 | 河北工业大学 | A kind of method of the full potassium W molecular sieve of gel-like solid phase method rapid synthesis |
| CN110330027A (en) * | 2019-07-31 | 2019-10-15 | 山东齐鲁华信实业股份有限公司 | Low silica-alumina ratio selects the production method of type molecular sieve ZSM-5 |
| CN112694101A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Core-shell molecular sieve, synthesis method and application thereof |
| CN114804142A (en) * | 2022-04-27 | 2022-07-29 | 西安建筑科技大学 | Method for preparing coal gangue-based ZSM-5 molecular sieve by using alkaline paper pulp waste liquid as template |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001680A (en) * | 2010-12-15 | 2011-04-06 | 岳阳怡天化工有限公司 | Method for preparing nano ZSM-5 molecular sieve |
| CN102874842A (en) * | 2012-10-26 | 2013-01-16 | 涟水水莲蓬新材料有限公司 | Preparation method of zsm-5 molecular sieve with small crystal grains and large crystal body |
| CN103803581A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | ZSM-5 composite molecular sieve with a core-shell structure and preparation method and application thereof |
| CN103880037A (en) * | 2012-12-20 | 2014-06-25 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and preparation method thereof |
| CN104085899A (en) * | 2014-07-24 | 2014-10-08 | 山东科技大学 | Template-free hydrothermal synthesis method of small crystal ZSM-5 molecular sieve |
| CN104340991A (en) * | 2013-07-29 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for preparing ZSM-5 zeolite molecular sieve, product and purpose thereof |
-
2017
- 2017-12-31 CN CN201711494447.9A patent/CN108033463A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001680A (en) * | 2010-12-15 | 2011-04-06 | 岳阳怡天化工有限公司 | Method for preparing nano ZSM-5 molecular sieve |
| CN102874842A (en) * | 2012-10-26 | 2013-01-16 | 涟水水莲蓬新材料有限公司 | Preparation method of zsm-5 molecular sieve with small crystal grains and large crystal body |
| CN103803581A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | ZSM-5 composite molecular sieve with a core-shell structure and preparation method and application thereof |
| CN103880037A (en) * | 2012-12-20 | 2014-06-25 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and preparation method thereof |
| CN104340991A (en) * | 2013-07-29 | 2015-02-11 | 中国科学院大连化学物理研究所 | Method for preparing ZSM-5 zeolite molecular sieve, product and purpose thereof |
| CN104085899A (en) * | 2014-07-24 | 2014-10-08 | 山东科技大学 | Template-free hydrothermal synthesis method of small crystal ZSM-5 molecular sieve |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179446A (en) * | 2018-09-28 | 2019-01-11 | 青岛大学 | A kind of hollow nano H-type ZSM-5 molecular sieve and preparation method thereof |
| CN109553114A (en) * | 2019-01-16 | 2019-04-02 | 河北工业大学 | A kind of method of the full potassium W molecular sieve of gel-like solid phase method rapid synthesis |
| CN110330027A (en) * | 2019-07-31 | 2019-10-15 | 山东齐鲁华信实业股份有限公司 | Low silica-alumina ratio selects the production method of type molecular sieve ZSM-5 |
| CN112694101A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Core-shell molecular sieve, synthesis method and application thereof |
| CN112694101B (en) * | 2019-10-23 | 2023-09-29 | 中国石油化工股份有限公司 | Core-shell molecular sieve, synthesis method and application thereof |
| CN114804142A (en) * | 2022-04-27 | 2022-07-29 | 西安建筑科技大学 | Method for preparing coal gangue-based ZSM-5 molecular sieve by using alkaline paper pulp waste liquid as template |
| CN114804142B (en) * | 2022-04-27 | 2023-09-01 | 西安建筑科技大学 | Method for preparing gangue-based ZSM-5 molecular sieve by taking alkaline paper pulp waste liquid as template |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108033463A (en) | The method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under no organic amine system | |
| CN103101924B (en) | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method | |
| CN101928011B (en) | Method for preparing ZSM-35 molecular sieve | |
| CN106938849A (en) | The method that the molecular sieves of ZSM 5 are synthesized using waste and old molecular sieve catalyst | |
| CN109701619A (en) | SSZ-13/SSZ-39 composite molecular sieves and its synthetic method | |
| CN102040228A (en) | Method for synthesizing MCM-22 molecular sieve | |
| CN105645427B (en) | The preparation method of the molecular sieves of ZSM 22 with mesoporous micropore graded structure | |
| CN107010636A (en) | A kind of ferrierite molecular sieve and preparation method and application | |
| CN102874833A (en) | Synthesis method of ZSM-48 molecular sieve | |
| CN102225772A (en) | Method for utilizing molecular sieve systhesis mother liquor | |
| CN103121698A (en) | Method for synthesizing SAPO (silicoaluminophosphate)-34 by solid-phase grinding | |
| CN102910645A (en) | Isomorphous phase compound molecular sieve and preparation method thereof | |
| CN108946761A (en) | A kind of preparation method and application of high dispersive ZSM-5 molecular sieve | |
| CN102502682B (en) | Mordenite preparation method | |
| WO2016145619A1 (en) | Method for preparation of, and application of, mordenite having mesopores and micropores | |
| CN110342538A (en) | A kind of synthetic method and its application of little crystal grain silicoaluminophosphate SAPO-34 molecular sieve | |
| CN101508446A (en) | Production process of regulating and controlling SAPO-11 molecular sieve bore diameter | |
| CN102441425B (en) | Preparation method for Y/MCM-41 composite molecular sieve | |
| US20180029894A1 (en) | Preparation method for beta zeolite | |
| CN105645428B (en) | The preparation method of the molecular sieves of SSZ 32 with mesoporous micropore graded structure | |
| CN110354874A (en) | The preparation method of the sial phosphorus carrier hydrogenation catalyst of porous structure and preparing the application in bio-fuel | |
| CN103708491B (en) | The method of synthesis IM-5 molecular sieve | |
| CN105268475B (en) | The method that n-butene skeletal isomerization prepares isobutene | |
| CN102050466B (en) | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material | |
| CN107020145B (en) | Mesoporous IM-5 molecular sieve and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180515 |
|
| RJ01 | Rejection of invention patent application after publication |