CN101525141A - Method for preparing SAPO-34 molecular sieve - Google Patents
Method for preparing SAPO-34 molecular sieve Download PDFInfo
- Publication number
- CN101525141A CN101525141A CN200910058831A CN200910058831A CN101525141A CN 101525141 A CN101525141 A CN 101525141A CN 200910058831 A CN200910058831 A CN 200910058831A CN 200910058831 A CN200910058831 A CN 200910058831A CN 101525141 A CN101525141 A CN 101525141A
- Authority
- CN
- China
- Prior art keywords
- sapo
- molecular sieve
- temperature
- preparation
- crystallization
- 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.)
- Granted
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for preparing SAPO-34 molecular sieve, which is characterized in that Al2O3, P2O5, SiO2, R and H2O which have the mol ratio of 1:0.5-1.02:0.1-0.8:0.32-3:50-200 are mixed together into crystallization liquid and processed by aging treatment at the temperature of 2-110 DEG C for 10-24hr; or the crystallization liquid is processed by ultrasonic treatment at the temperature of 20-90 DEG C for 0.5-1hr, the ultrasonic frequency is 40-60 Hz, and the power is 200-400W. After being pretreated by the technique, the crystallization liquid is crystallized at the temperature of 180-200 DEG C for 18-48hr, and the solid product is washed in a centrifugal way and dried at the temperature of 105-115 DEG C; then, the obtained solid product is calcined at the temperature of 530-560 DEG C for 5-6hr, so that the SAPO-34 molecular sieve is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of SAPO-34 molecular sieve, belong to the Preparation of Catalyst field.
Background technology
Low-carbon alkene (referring to the mixture of ethene, propylene, butylene and their preparations here) as the starting material of synthetic detergent, plastics, fiber and all kinds of chemical materialss, plays a part very important in modern petrochemical complex industry.Traditional light olefin is produced by petroleum cracking, that is to say that our present most chemical industry raw material and fuel all depend on oil.Petroleum resources are very poor in China, and China's petrochemical industry is subjected to international petroleum price change factor affecting bigger.
From the energy structure of China, the process that changes C1 raw material (methyl alcohol, methyl chloride etc.) into light olefin by non-conventional oil resources such as Sweet natural gas and the coals breach that to be the Essential Chemistry product break away under the state that depends on oil.In this process, the SAPO-34 molecular sieve occupies a critical role.Because SAPO-34 is the octatomic ring structure, the aperture is about 0.43nm, and this has just limited C
1The gaseous product that transforms has only C
1, C
2, C
3Hydro carbons.Though in the SAPO-34 crystal, there is the C of side chain
4And C
5Saturated hydrocarbons as Trimethylmethane and iso-pentane, can not leave crystal but their volume is too big, and their existence forms the additional space steric hindrance again to the diffusion of long linear hydrocarbon.So have C only
2And C
3Hydro carbons can diffuse out outside the crystal at an easy rate, and this just makes SAPO-34 to C
1Transform the system light olefin and have good selectivity.
U.S. Pat 4440871 discloses the preparation method of multiple silicoaluminophosphamolecular molecular sieves.Adopt silicon source, phosphorus source, aluminium source and organic formwork agent to produce the preparation method of SAPO-34 molecular sieve, the crystallization time of this method is long, reaches 150hr even more than the 330hr.
Chinese patent CN1088483 discloses the method for the synthetic SAPO-34 molecular sieves of one or more cheap organic formwork agents, and this method is used for synthesizing the SAPO-34 molecular sieve of big crystal grain (＞10 μ m).
Chinese patent CN101293660 discloses a kind of method of controlling the synthetic SAPO molecular sieve of order of addition(of ingredients), but the order of addition(of ingredients) operation is too complicated.
Above-mentioned patent documentation is reported the synthetic of SAPO-34 molecular sieve, but these patents are synthesizing high-crystallinity, uniform particle diameter, and also there is more defective in the SAPO-34 molecular sieve aspect of little crystal grain, compels to wait to improve.
Summary of the invention
The objective of the invention is to provide a kind of preparation method of SAPO-34 molecular sieve, be characterized in before the crystallization crystallization liquid being carried out low temperature maturation or ultrasonic pretreatment at the deficiencies in the prior art, and then the crystallization calcining, prepare the SAPO-34 molecular sieve.It is even that the SAPO-34 molecular sieve of preparation has particle diameter, and crystal grain is little, the characteristics that degree of crystallinity is high.
Ultrasonic technology can cause a kind of unusual important effect---cavatition when acting on the liquid medium as a kind of physical instrument and means.Cavitation is meant the dynamic process that the micro-bubble (cavitation nucleus) that is present in the liquid vibrates, grows and collapse under the effect of sound field, when cavitation bubble collapsed, the part can produce above high temperature of 5000K and the above high pressure of 500atm, and rate of temperature change is up to 10
9Ks
-1, and accompanying by intensive shockwave and speed per hour jet up to 400km, such condition can be some chemical reactions and opens new passage.Through the crystallization liquid after the supersound process, because the localized hyperthermia of ultrasonic generation and the dissolving that high pressure has promoted aluminium source and silicon source help the appearance and the increase of the silicoaluminate radical ion of nucleation, nucleus quantity increases, improve degree of crystallinity, be easy to form the little and uniform molecular sieve crystal of granularity.
Molecular sieve forms and comprises the formation of nucleus and two stages of growth of nucleus.Wherein low temperature is the formation that helps nucleus, and high temperature helps the growth of nucleus.Adopt aged at a lower temperature method earlier to increase the formation power of nucleus, treat to promote down in comparatively high temps again after nucleus quantity increases the growth of nucleus, also be beneficial to the degree of crystallinity that improves molecular sieve, the little and uniform molecular sieve crystal of formation granularity.
Purpose of the present invention is realized by following technical measures:
The preparation method's of SAPO-34 molecular sieve starting raw material is composed of the following components, is calculated in molar ratio as:
Al
2O
3: P
2O
5: SiO
2: R: H
2O=1: 0.5～1.02: 0.1～0.8: 0.32～3: 50～200, wherein R is an organic formwork agent, and prepares by following processing step and processing parameter:
(1), the pre-treatment of crystallization liquid
With Al
2O
3: P
2O
5: SiO
2: R: H
2O=1: 0.5～1.02: 0.1～0.8: 0.32～3: the mixing of materials of 50～200 mol ratios becomes crystallization liquid, handles 10～24hr in 2～110 ℃ of ageings of temperature; Perhaps with above-mentioned crystallization liquid in 20～90 ℃ of ultrasonication 0.5～1hr of temperature, ultrasonic frequency 40～60Hz, power 200～400W.
(2), the preparation of SAPO-34 molecular sieve
In 180～200 ℃ of crystallization 18～48hr of temperature, the centrifuge washing solid product through 105～115 ℃ of drying 2～3hr of temperature, is calcined 5～6hr with solid product for 530～560 ℃ in temperature again, obtains the SAPO-34 molecular sieve with the pretreated crystallization liquid of above-mentioned technology.
Al
2O
3The aluminium source be in activated alumina, pseudo-boehmite or the aluminum alkoxide etc. any;
P
2O
5The phosphorus source be ortho-phosphoric acid;
SiO
2The silicon source be in silicon sol, active silica or the positive silicon ester etc. any;
Organic formwork agent is at least a in triethylamine, tetraethyl ammonium hydroxide, diethylamine, Tetramethylammonium hydroxide, diethanolamine or the morpholine.
Handle the molecular sieve that obtains behind the crystallization liquids with two kinds of pretreatment modes respectively, detect and calculate with XRD, degree of crystallinity is more than 90%, C
2～3Selectivity of light olefin more than 85%.
The present invention has following advantage:
1, crystallization time is shorter, and crystallization time is 18～48hr, the degree of crystallinity height;
2, the SAPO-34 molecular sieve epigranular that obtains, and particle diameter is little;
3, the process of preparation crystallization liquid is simpler, easy to operate.
Embodiment
Below by specific embodiments the present invention is carried out concrete description; be necessary to be pointed out that at this implementing example only is used for the present invention is further specified; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
Aluminum isopropylate 15.1g (0.074mol) and deionized water 27.89g (1.55mol) are mixed the back add 85% ortho-phosphoric acid 8.69g (0.075mol), add triethylamine 11.23g (0.11mol) and 30% silicon sol 5.87g (0.029mol) after stirring successively, fully stir.Said mixture is packed in the pressure vessel of inner liner polytetrafluoroethylene, and in 20 ℃ of temperature, frequency 40kHz is behind the power 200W supersound process 0.5hr, in 200 ℃ of crystallization 18hr of temperature.The centrifuge washing solid product in 110 ℃ of dry 3hr of temperature, obtains the SAPO-34 zeolite product with dried solid product in 550 ℃ of calcinings of temperature 6hr then.Recording product degree of crystallinity is 93%, and median size is 3.7 μ m.
Embodiment 2
With Al
2O
3Content is that 66% pseudo-boehmite 5.72g (0.037mol) adds among the 10wt% tetraethyl ammonium hydroxide aqueous solution 17.43g (0.012mol), mix the back and slowly drip 85% ortho-phosphoric acid 4.26g (0.037mol), and adding deionized water 100g (5.56mol) stirs, add 30% silicon sol 1.10g (0.0055mol) and deionized water 11.51g (0.64mol) then, fully stir.Above-mentioned system is packed in the pressure vessel of tetrafluoroethylene, and in 90 ℃ of temperature, frequency 60kHz is behind the power 400W supersound process 1hr, in 180 ℃ of crystallization 48hr of temperature.The centrifuge washing solid product in 115 ℃ of dry 2.5hr of temperature, obtains the SAPO-34 zeolite product with dried solid product in 545 ℃ of calcinings of temperature 6hr then.Recording product degree of crystallinity is 95%, and median size is 1.1 μ m.
Embodiment 3
With Al
2O
3Content is that 66% pseudo-boehmite 5.72g (0.037mol) adds among the 10wt% tetraethyl ammonium hydroxide aqueous solution 33.87g (0.023mol), the back adding 30% silicon sol 4.40g (0.022mol) that stirs fully stirs, and slowly drips 85% ortho-phosphoric acid 8.52g (0.074mol) and deionized water 43.13g (2.4mol) then and mixes.Above-mentioned system is packed in the pressure vessel of tetrafluoroethylene, behind 80 ℃ of pre-crystallization 24hr of temperature, in 200 ℃ of crystallization 24hr of temperature.The centrifuge washing solid product in 105 ℃ of dry 3hr of temperature, obtains the SAPO-34 zeolite product with dried solid product in 560 ℃ of calcinings of temperature 5hr then.Recording product degree of crystallinity is 98%, and median size is 2.7 μ m.
Embodiment 4
Getting aluminum isopropylate 15.1g (0.074mol) mixes with deionized water 41.39g (2.30mol), add 85% ortho-phosphoric acid 6.82g (0.059mol) then, add triethylamine 5.62g (0.056mol), 10wt% tetraethyl ammonium hydroxide aqueous solution 21.79g (0.015mol) and 30% silicon sol 2.20g (0.01mol) after stirring successively, and fully stir.Above-mentioned system is packed in the pressure vessel of inner liner polytetrafluoroethylene, prior to 110 ℃ of pre-crystallization 12hr of temperature, again in 2 ℃ of ageing 8hr of temperature, at last in 200 ℃ of crystallization 18hr of temperature.The centrifuge washing solid product in 110 ℃ of dry 3hr of temperature, obtains the SAPO-34 zeolite product with dried solid product in 540 ℃ of calcinings of temperature 6hr then.Recording product degree of crystallinity is 99%, and median size is 4.2 μ m.
Claims (7)
1, a kind of preparation method of SAPO-34 molecular sieve is characterized in that the starting raw material of this method is composed of the following components, is calculated in molar ratio as:
Al
2O
3: P
2O
5: SiO
2: R: H
2O=1: 0.5～1.02: 0.1～0.8: 0.32～3: 50～200, wherein R is an organic formwork agent, and prepares by following processing step and processing parameter:
(1), the pre-treatment of crystallization liquid
With Al
2O
3: P
2O
5: SiO
2: R: H
2O=1: 0.5～1.02: 0.1～0.8: 0.32～3: the mixing of materials of 50～200 mol ratios becomes crystallization liquid, handles 10～24hr in 2～110 ℃ of ageings of temperature; Perhaps with above-mentioned crystallization liquid in 20～90 ℃ of ultrasonication 0.5～1hr of temperature, ultrasonic frequency 40～60Hz, power 200～400W;
(2), the preparation of SAPO-34 molecular sieve
In 180～200 ℃ of crystallization 18～48hr of temperature, the centrifuge washing solid product through 105～115 ℃ of drying 2～3hr of temperature, is calcined 5～6hr with solid product for 530～560 ℃ in temperature then, obtains the SAPO-34 molecular sieve with the pretreated crystallization liquid of above-mentioned technology.
2, the preparation method of SAPO-34 molecular sieve according to claim 1 is characterized in that Al
2O
3The aluminium source be in activated alumina, pseudo-boehmite or the aluminum alkoxide etc. any.
3, the preparation method of SAPO-34 molecular sieve according to claim 1 is characterized in that P
2O
5The phosphorus source be ortho-phosphoric acid.
4, the preparation method of SAPO-34 molecular sieve according to claim 1 is characterized in that SiO
2The silicon source be in silicon sol, active silica or the positive silicon ester etc. any.
5, the preparation method of SAPO-34 molecular sieve according to claim 1 is characterized in that organic formwork agent is at least a in triethylamine, tetraethyl ammonium hydroxide, diethylamine, Tetramethylammonium hydroxide, diethanolamine and the morpholine.
6, the SAPO-34 molecular sieve for preparing as method as described in the claim 1～5.
7, the conversion producing light olefins C that is used for methyl alcohol or methyl chloride as SAPO-34 molecular sieve as described in the claim 6
2～3Catalyzed reaction, C
1Conversion of raw material is more than 90%, low-carbon alkene C
2～3Selectivity is more than 85%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100588313A CN101525141B (en) | 2009-04-03 | 2009-04-03 | Method for preparing SAPO-34 molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100588313A CN101525141B (en) | 2009-04-03 | 2009-04-03 | Method for preparing SAPO-34 molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101525141A true CN101525141A (en) | 2009-09-09 |
| CN101525141B CN101525141B (en) | 2012-02-08 |
Family
ID=41093242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100588313A Expired - Fee Related CN101525141B (en) | 2009-04-03 | 2009-04-03 | Method for preparing SAPO-34 molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101525141B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134081A (en) * | 2010-01-25 | 2011-07-27 | 天津海赛纳米材料有限公司 | Method for synthesizing SAPO-34 molecular sieve in absence of template agent |
| CN102464536A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for producing low carbon olefin |
| CN103332702A (en) * | 2013-06-22 | 2013-10-02 | 天津众智科技有限公司 | Preparation method of small-crystal-grain SAPO-34 molecular sieve |
| CN103408034A (en) * | 2013-06-22 | 2013-11-27 | 天津众智科技有限公司 | Preparation method of SAPO-34 molecular sieve with small average grain diameter |
| CN103420391A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Small grain SAPO-34 molecular sieve preparation method |
| CN106044794A (en) * | 2016-02-22 | 2016-10-26 | 山东齐鲁华信高科有限公司 | Preparation method of laminar SAPO-34 molecular sieve |
| CN106315610A (en) * | 2016-08-22 | 2017-01-11 | 天津大学 | Method for synthesizing CHA molecular sieve through ultrasonic pretreatment of coal gangue |
| US9550178B2 (en) | 2014-08-05 | 2017-01-24 | Sabic Global Technologies B.V. | Stable silicoaluminophosphate catalysts for conversion of alkyl halides to olefins |
| CN106698467A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Synthetic method of nano SAPO-34 molecular sieve |
| CN107570208A (en) * | 2017-08-31 | 2018-01-12 | 昆明理工大学 | A kind of preparation method and application of epoxidation catalysts |
| CN108298560A (en) * | 2018-03-12 | 2018-07-20 | 山西潞安煤基合成油有限公司 | A kind of method of ultrasonic wave added synthesis hierarchical porous structure SAPO-11 molecular sieves |
| CN108706609A (en) * | 2018-06-07 | 2018-10-26 | 深圳科冠华太新材料技术有限公司 | A kind of preparation method of nanometer of SAPO-34 molecular sieve |
| US10532350B2 (en) | 2014-08-22 | 2020-01-14 | W.R. Grace & Co.-Conn | Method for synthesizing silicoaluminophosphate-34 molecular sieves using monoisopropanolamine |
| CN111320186A (en) * | 2018-12-13 | 2020-06-23 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
| CN111960429A (en) * | 2020-08-26 | 2020-11-20 | 万华化学集团股份有限公司 | Preparation method of hierarchical porous aluminum phosphate molecular sieve catalyst, catalyst prepared by hierarchical porous aluminum phosphate molecular sieve catalyst and application of hierarchical porous aluminum phosphate molecular sieve catalyst in olefin isomerization |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100584758C (en) * | 2006-08-08 | 2010-01-27 | 中国科学院大连化学物理研究所 | Fast synthetic method for phosphorus-silicon-aluminum molecular sieve |
| CN101214974B (en) * | 2007-12-29 | 2012-01-04 | 南开大学 | Method for preparing small crystal grain SAPO-34 molecular screen |
-
2009
- 2009-04-03 CN CN2009100588313A patent/CN101525141B/en not_active Expired - Fee Related
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134081A (en) * | 2010-01-25 | 2011-07-27 | 天津海赛纳米材料有限公司 | Method for synthesizing SAPO-34 molecular sieve in absence of template agent |
| CN102464536A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for producing low carbon olefin |
| CN102464536B (en) * | 2010-11-17 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing low carbon olefin |
| CN103420391A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Small grain SAPO-34 molecular sieve preparation method |
| CN103420391B (en) * | 2012-05-16 | 2015-08-12 | 中国石油化工股份有限公司 | The preparation method of fine grain SAPO-34 molecular sieve |
| CN103332702A (en) * | 2013-06-22 | 2013-10-02 | 天津众智科技有限公司 | Preparation method of small-crystal-grain SAPO-34 molecular sieve |
| CN103408034A (en) * | 2013-06-22 | 2013-11-27 | 天津众智科技有限公司 | Preparation method of SAPO-34 molecular sieve with small average grain diameter |
| CN103408034B (en) * | 2013-06-22 | 2015-10-28 | 天津众智科技有限公司 | The preparation method of the SAPO-34 molecular sieve that median size is little |
| US9550178B2 (en) | 2014-08-05 | 2017-01-24 | Sabic Global Technologies B.V. | Stable silicoaluminophosphate catalysts for conversion of alkyl halides to olefins |
| US10532350B2 (en) | 2014-08-22 | 2020-01-14 | W.R. Grace & Co.-Conn | Method for synthesizing silicoaluminophosphate-34 molecular sieves using monoisopropanolamine |
| CN106698467A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Synthetic method of nano SAPO-34 molecular sieve |
| CN106698467B (en) * | 2015-11-12 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of synthetic method of nanometer of SAPO-34 molecular sieve |
| CN106044794A (en) * | 2016-02-22 | 2016-10-26 | 山东齐鲁华信高科有限公司 | Preparation method of laminar SAPO-34 molecular sieve |
| CN106044794B (en) * | 2016-02-22 | 2018-12-21 | 山东齐鲁华信高科有限公司 | A kind of preparation method of plate stratiform SAPO-34 molecular sieve |
| CN106315610A (en) * | 2016-08-22 | 2017-01-11 | 天津大学 | Method for synthesizing CHA molecular sieve through ultrasonic pretreatment of coal gangue |
| CN106315610B (en) * | 2016-08-22 | 2018-07-24 | 天津大学 | A kind of method of ultrasound pretreatment gangue synthesis CHA molecular sieves |
| CN107570208A (en) * | 2017-08-31 | 2018-01-12 | 昆明理工大学 | A kind of preparation method and application of epoxidation catalysts |
| CN107570208B (en) * | 2017-08-31 | 2020-08-25 | 昆明理工大学 | Preparation method and application of epoxidation reaction catalyst |
| CN108298560A (en) * | 2018-03-12 | 2018-07-20 | 山西潞安煤基合成油有限公司 | A kind of method of ultrasonic wave added synthesis hierarchical porous structure SAPO-11 molecular sieves |
| CN108706609A (en) * | 2018-06-07 | 2018-10-26 | 深圳科冠华太新材料技术有限公司 | A kind of preparation method of nanometer of SAPO-34 molecular sieve |
| CN108706609B (en) * | 2018-06-07 | 2021-07-30 | 深圳科冠华太新材料技术有限公司 | Preparation method of nano SAPO-34molecular sieve |
| CN111320186A (en) * | 2018-12-13 | 2020-06-23 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
| CN111960429A (en) * | 2020-08-26 | 2020-11-20 | 万华化学集团股份有限公司 | Preparation method of hierarchical porous aluminum phosphate molecular sieve catalyst, catalyst prepared by hierarchical porous aluminum phosphate molecular sieve catalyst and application of hierarchical porous aluminum phosphate molecular sieve catalyst in olefin isomerization |
| CN111960429B (en) * | 2020-08-26 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method of hierarchical porous aluminum phosphate molecular sieve catalyst, catalyst prepared by hierarchical porous aluminum phosphate molecular sieve catalyst and application of hierarchical porous aluminum phosphate molecular sieve catalyst in olefin isomerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101525141B (en) | 2012-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101525141B (en) | Method for preparing SAPO-34 molecular sieve | |
| CN102464338B (en) | Preparation method for silicoaluminophosphate (SAPO)-34 molecular sieve with small crystal particle | |
| CN104150507B (en) | One one-step preparation method of ghost type ZSM-5 molecular sieve with small crystal grains | |
| CN104556094B (en) | A kind of Y/Silicalite-1 composite molecular screen and preparation method thereof | |
| CN108927213A (en) | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane | |
| CN104556092B (en) | Hierarchical porous structure SAPO molecular sieve material and preparation method thereof | |
| CN104098106B (en) | The method of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 a kind of | |
| CN104556130B (en) | The method that vapor phase method synthesizes ZSM-5/Silicalite core-shell molecular sieves | |
| CN105800637B (en) | A kind of release alcohol preparation method of the high skeleton Ti content HTS of Fast back-projection algorithm | |
| Kim et al. | Sonochemical synthesis of zeolite A from metakaolinite in NaOH solution | |
| CN105819464A (en) | High yield rapid synthesis method of titanium-silicon molecular sieve TS-1 | |
| CN107500312A (en) | A kind of fluorine richness molecular sieve H ZSM 35 and preparation method thereof | |
| CN110026234A (en) | A kind of alkylation catalyst and its preparation method and application | |
| CN106268926A (en) | A kind of MCM-22 molecular sieve with multistage pore canal and its preparation method and application | |
| CN102198950B (en) | Method for preparing NaY molecular sieve with high aluminum-silicon ratio | |
| CN103420391B (en) | The preparation method of fine grain SAPO-34 molecular sieve | |
| CN104386707A (en) | Synthesis method of ultralow-sodium high-silicon nano ZSM-5 molecular sieve | |
| CN101993091B (en) | Method for synthesizing ZSM-5 zeolite | |
| CN110240177A (en) | A kind of laminated structure MFI type zeolite molecular sieve and preparation method thereof | |
| CN103848437A (en) | Preparation method of ZSM-5 molecular sieve | |
| CN108658087A (en) | A kind of multistage pore canal TS-1 zeolitic materials and preparation method thereof | |
| CN110038627A (en) | A kind of synthetic method of multi-stage porous ZSM-5 molecular sieve anchoring Pd nano particle | |
| CN205683998U (en) | A kind of ultrasonic atomization micro-wave digestion synergism reactor | |
| CN106276967B (en) | A kind of synthetic method of mesoporous zeolite | |
| CN106946267B (en) | A kind of EU-1 molecular sieve and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120208 Termination date: 20150403 |
|
| EXPY | Termination of patent right or utility model |