CN114702463A - Method for preparing methyl epichlorohydrin - Google Patents
Method for preparing methyl epichlorohydrin Download PDFInfo
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- CN114702463A CN114702463A CN202210317516.3A CN202210317516A CN114702463A CN 114702463 A CN114702463 A CN 114702463A CN 202210317516 A CN202210317516 A CN 202210317516A CN 114702463 A CN114702463 A CN 114702463A
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- catalyst
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- deionized water
- molecular sieve
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention discloses a method for preparing methyl epichlorohydrin, which is characterized in that methyl allyl chloride and hydrogen peroxide are subjected to epoxidation reaction under the catalysis of a catalyst to obtain methyl epichlorohydrin, wherein the catalyst is a P-SBA-15 molecular sieve. Up to methallyl chloride to H2O2The conversion of (a) is higher than 95%, and the selectivity of methyl epichlorohydrin to methallyl chloride is 94%. The catalyst adopts a molecular sieve loading method, so that active components are uniformly dispersed, the stability of the catalyst can be improved, the loss of active substances is reduced, the catalyst is green and environment-friendly, the catalyst is convenient to recover after the reaction is finished, high activity is still maintained through calcination regeneration, and the economic benefit is further improved.
Description
Technical Field
The invention relates to the field of synthesis of organic chemical materials, and in particular relates to a method for preparing methyl epichlorohydrin.
Background
Methyl epichlorohydrin is an important organic chemical raw material and intermediate. The methyl allyl chloride is catalyzed and epoxidized by a catalyst to generate methyl epichlorohydrin, and the catalytic effect and the recovery of the catalyst are particularly important. Specifically, the existing method mainly adopts quaternary ammonium phosphotungstic acid and T i-1 molecular sieve catalyst, and hydrogen peroxide is used as a main oxygen source. The recovery mode of the catalyst is as follows: : and (3) cooling the reaction solution after the reaction to a lower temperature, separating out the catalyst, and centrifuging. The molecular sieve has smaller particles and can be partially dissolved in the reaction liquid, so that the recovery rate of the catalyst is low; the molecular sieve has pore channels, and after the reaction, partial pore channels can be blocked, so that the activity of the catalyst is reduced after the catalyst is recovered.
WO prepared according to the invention3the/P-SBA-15 solid acid catalyst is a catalyst which takes a mesoporous molecular sieve as a carrier, has higher specific surface area, has higher catalytic effect and methyl epichlorohydrin selective effect on epoxidation, can be recovered only by filtering after the reaction is finished, and still has higher catalytic activity after being regenerated by drying and calcining.
Disclosure of Invention
The invention aims to provide a method for preparing methyl epichlorohydrin, which takes mesoporous molecular sieve SBA-15 as a carrier, phosphoric acid acidification and sodium tungstate loading are added to the carrier to be used as a catalyst, hydrogen peroxide is used as an oxygen source, and methyl epichlorohydrin is prepared from methyl allyl chloride. The method can be used under the condition of no solvent, and the catalyst is easy to recycle, and has higher conversion rate of hydrogen peroxide and selectivity of methyl epichlorohydrin.
The purpose of the invention is realized by the following technical scheme:
the method for preparing the methyl epichlorohydrin catalyzes the methyl allyl chloride and the H by the prepared catalyst2O2Epoxidation reaction is carried out to obtain methyl epichlorohydrin.
Preferably, in the method, the catalyst is obtained by preparing the P-SBA-15 molecular sieve by a hydrothermal method, and then impregnating and drying.
The preparation method of the catalyst specifically comprises the following steps:
s1, firstly melting a triblock copolymer P123, then pouring into a polytetrafluoroethylene reaction kettle, adding 85% phosphoric acid and deionized water, and stirring in a water bath at 38 ℃ until the P123 is completely dissolved;
s2, adding tetraethoxysilane, keeping the reaction temperature, and continuously stirring for 4-6 hours to obtain a reaction solution;
s3, pouring the reaction liquid into a sealed tank lined with polytetrafluoroethylene, and crystallizing for 48-72 hours in an oven at 100 ℃;
s4, naturally cooling to room temperature after crystallization, performing suction filtration, washing with deionized water to weak acidity, drying the obtained filter cake in a drying oven at 100 ℃ for 12 hours, and performing temperature programming in a muffle furnace to 500 ℃ for calcination for 4-6 hours;
s5, uniformly mixing the molecular sieve obtained from a4 with silica sol in a ratio of 5:1, and then granulating and baking to obtain a granular catalyst;
s6, dissolving a certain amount of sodium tungstate in deionized water, wherein the mass ratio of the deionized water to the catalyst is 10:1, pouring the granular catalyst, uniformly mixing, soaking for 4 hours, and drying in an oven to obtain the epoxidation catalyst.
Preferably, in the method, the mass ratio of the P123 to the 85% phosphoric acid to the ethyl orthosilicate to the sodium tungstate is 10:25:15: 1.
Preferably, in the method, the using amount of the catalyst is 2-5 wt% of the total mass of the methallyl chloride and the hydrogen peroxide.
Preferably, in the process, methallyl chloride is reacted with H2O2The amount ratio of the substances (A) is 1:0.5-1.1.
Preferably, in the method, the reaction temperature is controlled between 40 and 70 ℃.
Preferably, in the method, the reaction time is 3-6 h.
It is also an object of the present invention to provide a process for the preparation of the above-described P-SBA-15 molecular sieve.
Compared with the prior art, the invention has the following advantages:
the method for preparing the methyl epichlorohydrin can ensure that the maximum methyl allyl chloride can be H2O2The conversion of (a) is higher than 95%, and the selectivity of methyl epichlorohydrin to methallyl chloride is 94%. The catalyst adopts a molecular sieve loading method, so that the active components are uniformly dispersed, the stability of the catalyst can be improved, the loss of active substances can be reduced, and the catalyst is green and environment-friendly. In addition, the active components of the catalyst are dispersed in the framework or pore canal of SBA-15, and the catalyst is granulated into particles, so that the catalyst is easy to deposit, difficult to dissolve and easy to recover; the catalyst is high temperature resistant, and through calcination, the blocking matter in the pore channel can be removed, the activity is recovered again, and the economic benefit is further improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples and comparative examples.
The definition formula of the conversion rate of hydrogen peroxide in the examples and the comparative examples is as follows:
definition of selectivity to epichlorohydrin in examples and comparative examples formula:
comparative example definition of catalyst recovery formula:
comparative example:
80g of methallyl chloride and 4.02g of T i-1 catalyst are added into a 250mL four-neck flask, the temperature is raised to 40 ℃, 54.1g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 60 ℃, and the reaction is continued for 5 hours after the dripping is finished. After the reaction, the reaction solution was centrifuged, and the organic layer was analyzed by gas phase, whereby the conversion of methallyl chloride was 95.1% and the selectivity of methylepichlorohydrin was 93.5%. The catalyst was recovered at a recovery rate of 62.2%.
The recovered catalyst was reacted under the same conditions, and the organic layer was analyzed in a vapor phase, whereby the conversion of methallyl chloride was 63.2% and the selectivity of methylepichlorohydrin was 92.5%.
Example 1:
adding 80g of methallyl chloride and 2.20g of catalyst into a 250mL four-neck flask, heating to 40 ℃, slowly dropwise adding 30.1g of 50% hydrogen peroxide while stirring, controlling the reaction temperature to be 40 ℃, and continuing to react for 3 hours after dropwise adding. After the reaction, the reaction solution was centrifuged, the organic layer was analyzed in a gas phase, and the catalyst was recovered.
The catalyst is obtained by soaking and drying a P-SBA-15 molecular sieve prepared by a hydrothermal method.
The preparation method of the specific catalyst comprises the following steps:
s1, firstly melting a triblock copolymer P123, then pouring into a polytetrafluoroethylene reaction kettle, adding 85% phosphoric acid and deionized water, and stirring in a water bath at 38 ℃ until the P123 is completely dissolved;
s2, adding tetraethoxysilane, keeping the reaction temperature, and continuously stirring for 4-6 hours to obtain a reaction solution;
s3, pouring the reaction liquid into a sealed tank lined with polytetrafluoroethylene, and crystallizing for 48-72 hours in an oven at 100 ℃;
s4, naturally cooling to room temperature after crystallization, performing suction filtration, washing with deionized water to weak acidity, drying the obtained filter cake in a drying oven at 100 ℃ for 12 hours, and performing temperature programming in a muffle furnace to 500 ℃ for calcination for 4-6 hours;
s5, uniformly mixing the molecular sieve obtained from a4 with silica sol in a ratio of 5:1, and then granulating and baking to obtain a granular catalyst;
s6, dissolving a certain amount of sodium tungstate in deionized water, wherein the mass ratio of the deionized water to the catalyst is 10:1, pouring the granular catalyst, uniformly mixing, soaking for 4 hours, and drying in an oven to obtain the epoxidation catalyst.
Wherein the mass ratio of P123, 85% phosphoric acid, ethyl orthosilicate and sodium tungstate is 10:25:15: 1.
Example 2:
adding 80g of methallyl chloride and 3.66g of catalyst into a 250mL four-neck flask, heating to 40 ℃, slowly dropwise adding 42.1g of 50% hydrogen peroxide while stirring, controlling the reaction temperature to be 50 ℃, and continuing to react for 4 hours after dropwise adding. After the reaction, the reaction solution was centrifuged, the organic layer was analyzed in a gas phase, and the catalyst was recovered.
Example 3:
in a 250mL four-neck flask, 80g of methallyl chloride and 5.36g of the catalyst described in the example were added, the temperature was raised to 40 ℃, 54.1g of 50% hydrogen peroxide was slowly added dropwise with stirring, the reaction temperature was controlled at 60 ℃, and after the dropwise addition, the reaction was continued for 5 hours. After the reaction, the reaction solution was centrifuged, the organic layer was analyzed in a gas phase, and the catalyst was recovered.
Example 4:
80g of methallyl chloride and 7.31g of the catalyst described in the example are added into a 250mL four-neck flask, the temperature is raised to 40 ℃, 66.1g of 50% hydrogen peroxide is slowly added dropwise with stirring, the reaction temperature is controlled to be 70 ℃, and after the dropwise addition is finished, the reaction is continued for 6 hours. After the reaction, the reaction solution was centrifuged, the organic layer was analyzed in a gas phase, and the catalyst was recovered.
Example 5:
in a 250mL four-neck flask, 80g of methallyl chloride and 4.02g of the catalyst described in the example were added, the temperature was raised to 40 ℃, 54.1g of 50% hydrogen peroxide was slowly added dropwise with stirring, the reaction temperature was controlled at 60 ℃, and after the dropwise addition, the reaction was continued for 5 hours. After the reaction, the reaction solution was centrifuged, the organic layer was analyzed in a gas phase, and the catalyst was recovered. And (3) reacting the recovered catalyst under the same conditions, taking the organic layer for gas phase analysis, recovering the catalyst, repeating the steps for three times, taking the catalyst recovered at the last time, calcining the catalyst in a muffle furnace at 550 ℃, repeating the reaction for one time, and taking the organic layer for gas phase analysis. The results after catalyst reuse and calcination regeneration are shown in the following table.
Experimental group number | Methallyl chloride conversion/%) | Methyl epichlorohydrin selectivity/%) |
Fresh catalyst | 95.2 | 94.2 |
Repeating for the first time | 94.9 | 94.4 |
Repeating for the second time | 94.7 | 94.5 |
Repeating for the third time | 93.5 | 95.1 |
Regenerated catalyst | 95.4 | 94.1 |
According to the above embodiment, the method for preparing methyl epichlorohydrin provided by the invention can obtain methyl epichlorohydrin with high efficiency and high selectivity, and can recycle the catalyst for multiple times, so that the method is an environment-friendly technical route.
Claims (9)
1. The method for preparing the methyl epichlorohydrin is characterized in that a catalyst is used for catalyzing methyl allyl chloride to perform epoxidation reaction with hydrogen peroxide to obtain the methyl epichlorohydrin, wherein the catalyst is a P-SBA-15 molecular sieve.
2. Process for manufacturing methylepichlorohydrin according to claim 1 characterised in that the process for manufacturing the molecular sieve P-SBA-15 is as follows:
s1, firstly melting a triblock copolymer P123, then pouring the triblock copolymer P123 into a polytetrafluoroethylene reaction kettle, adding 85% phosphoric acid and deionized water, and placing the polytetrafluoroethylene reaction kettle in a 38 ℃ water bath for stirring until the P123 is completely dissolved;
s2, adding tetraethoxysilane, keeping the reaction temperature, and continuously stirring for 4-6 hours to obtain a reaction solution;
s3, pouring the reaction liquid into a sealed tank lined with polytetrafluoroethylene, and crystallizing for 48-72 hours in an oven at 100 ℃;
s4, naturally cooling to room temperature after crystallization, performing suction filtration, washing with deionized water to weak acidity, drying the obtained filter cake in a drying oven at 100 ℃ for 12 hours, and performing temperature programming in a muffle furnace to 500 ℃ for calcination for 4-6 hours;
s5, uniformly mixing the molecular sieve obtained from a4 with silica sol in a ratio of 5:1, and then granulating and baking to obtain a granular catalyst;
s6, dissolving sodium tungstate in deionized water, pouring the granular catalyst according to the mass ratio of the deionized water to the catalyst of 10:1, uniformly mixing, soaking for 4 hours, and drying in an oven to obtain the epoxidation catalyst.
3. The method for preparing the catalyst according to claim 2, wherein the mass ratio of the P123 to the 85% phosphoric acid to the ethyl orthosilicate to the sodium tungstate is 10:25:15: 1.
4. The method for preparing methyl epichlorohydrin according to any one of claims 1 to 3 wherein the amount of the catalyst is 2 to 5 wt% of the total mass of the methallyl chloride and the hydrogen peroxide.
5. The process for preparing methyl epichlorohydrin according to claim 1, wherein the mass ratio of the methallyl chloride to the hydrogen peroxide is 1:0.5-1.1.
6. Process for manufacturing methyl epichlorohydrin according to claim 1 or 5, characterized in that the reaction temperature of the epoxidation reaction is controlled between 40 and 70 ℃.
7. Process for the manufacture of methylepichlorohydrin according to claim 6, characterized in that the epoxidation reaction has a reaction time of from 3 to 6 h.
8. A preparation method of a P-SBA-15 molecular sieve is characterized by comprising the following steps:
s1, firstly melting a triblock copolymer P123, then pouring the triblock copolymer P123 into a polytetrafluoroethylene reaction kettle, adding 85% phosphoric acid and deionized water, and placing the polytetrafluoroethylene reaction kettle in a 38 ℃ water bath for stirring until the P123 is completely dissolved;
s2, adding tetraethoxysilane, keeping the reaction temperature, and continuously stirring for 4-6 hours to obtain a reaction solution;
a3. pouring the reaction liquid into a sealed tank with a polytetrafluoroethylene lining, and crystallizing for 48-72h in an oven at 100 ℃;
s4, naturally cooling to room temperature after crystallization, performing suction filtration, washing with deionized water to weak acidity, drying the obtained filter cake in a drying oven at 100 ℃ for 12 hours, and performing temperature programming in a muffle furnace to 500 ℃ for calcination for 4-6 hours;
s5, uniformly mixing the molecular sieve obtained from a4 with silica sol in a ratio of 5:1, and then granulating and baking to obtain a granular catalyst;
s6, dissolving sodium tungstate in deionized water, pouring the granular catalyst according to the mass ratio of the deionized water to the catalyst of 10:1, uniformly mixing, soaking for 4 hours, and drying in an oven to obtain the epoxidation catalyst.
9. The preparation method of the catalyst according to claim 8, wherein the mass ratio of the P123, the 85% phosphoric acid, the ethyl orthosilicate and the sodium tungstate is 10:25:15: 1.
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11171880A (en) * | 1997-12-05 | 1999-06-29 | Daiso Co Ltd | Epoxidation of halogenated allyls and regeneration of used catalyst |
PL358761A1 (en) * | 2003-02-17 | 2004-08-23 | Politechnika Szczecińska | Method for receiving 2-methylglycerine epichlorohydrin |
CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
CN101205220A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of methyl epichlorohydrin |
JP2010100546A (en) * | 2008-10-22 | 2010-05-06 | Daiso Co Ltd | Method for epoxidizing olefin compound |
CN102464632A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane |
CN110170327A (en) * | 2019-05-21 | 2019-08-27 | 南京工业大学 | A kind of mesoporous C/SiO2Carried heteropoly acid catalyst and its preparation method and application |
CN111514924A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for catalytic synthesis of long-chain alkyl aromatic hydrocarbon |
CN112076778A (en) * | 2020-09-29 | 2020-12-15 | 浙江皇马科技股份有限公司 | Catalyst raw powder, catalyst, preparation method and application |
-
2022
- 2022-03-29 CN CN202210317516.3A patent/CN114702463A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11171880A (en) * | 1997-12-05 | 1999-06-29 | Daiso Co Ltd | Epoxidation of halogenated allyls and regeneration of used catalyst |
PL358761A1 (en) * | 2003-02-17 | 2004-08-23 | Politechnika Szczecińska | Method for receiving 2-methylglycerine epichlorohydrin |
CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
CN101205220A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of methyl epichlorohydrin |
JP2010100546A (en) * | 2008-10-22 | 2010-05-06 | Daiso Co Ltd | Method for epoxidizing olefin compound |
CN102464632A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane |
CN110170327A (en) * | 2019-05-21 | 2019-08-27 | 南京工业大学 | A kind of mesoporous C/SiO2Carried heteropoly acid catalyst and its preparation method and application |
CN111514924A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for catalytic synthesis of long-chain alkyl aromatic hydrocarbon |
CN112076778A (en) * | 2020-09-29 | 2020-12-15 | 浙江皇马科技股份有限公司 | Catalyst raw powder, catalyst, preparation method and application |
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