CN109126860B - Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve - Google Patents
Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve Download PDFInfo
- Publication number
- CN109126860B CN109126860B CN201810945900.1A CN201810945900A CN109126860B CN 109126860 B CN109126860 B CN 109126860B CN 201810945900 A CN201810945900 A CN 201810945900A CN 109126860 B CN109126860 B CN 109126860B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mesoporous molecular
- stirring
- solution
- ultraviolet light
- 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.)
- Active
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to preparation of a mesoporous molecular sieve, and discloses a method for preparing an acidic mesoporous molecular sieve by using hydrogen peroxide and application of the acidic mesoporous molecular sieve. The preparation method provided by the invention improves the acidity of the mesoporous molecular sieve by adding ultraviolet light and hydrogen peroxide in the preparation process of the mesoporous molecular sieve. The preparation method makes the mesoporous molecular sieve acidic, increases active sites, and can improve the catalytic activity of the mesoporous molecular sieve, and because metal heteroatoms are not introduced to modulate the acidity of the molecular sieve, the introduction of active components is not existed, the falling of the active components can not occur, the stability of the molecular sieve is increased, and the industrial production of the molecular sieve is realized.
Description
Technical Field
The invention relates to preparation of a molecular sieve, in particular to a method for preparing an acidic mesoporous molecular sieve by utilizing hydrogen peroxide and application of the acidic mesoporous molecular sieve.
Background
The novel mesoporous molecular sieve M41S has been developed successfully, and has a large uniform pore channel structure, so that the mesoporous molecular sieve has a good application prospect when being used as a catalyst for macromolecular reaction. However, due to the complexity and uncontrollable nature of the synthetic chemistry, such as the type of template agent, the silica-alumina ratio, the system pH, the crystallization temperature and the crystallization time, the shape and the structure of the synthesized mesoporous molecular sieve can be influenced; except that the surface silicon hydroxyl has weak acidity, the mesoporous molecular sieve basically does not show any acidity, lacks active sites and has weak catalytic oxidation reaction capability, so the application of the mesoporous molecular sieve in catalysis is limited, and the insufficient acidity severely restricts the industrial application of the mesoporous molecular sieve.
Most of the existing researches modulate the acidity of a molecular sieve by introducing metal heteroatoms into a molecular sieve framework to enable the molecular sieve to meet the requirement of acid catalysis, for example, introducing metal components such as Al, Ti and the like into a pure silicon molecular sieve to catalyze phenol friedel-crafts alkylation reaction to prepare alkylbenzene; for example, the supported metallocene on the hollow spherical mesoporous composite material catalyzes acrylic acid and methanol to obtain methyl acrylate; however, the stability of the molecular sieve is reduced by adding the metal and the active component, and the addition of the active component is unstable and easy to fall off, so that the industrial production of the molecular sieve is difficult to realize. Therefore, the preparation method of the acidic mesoporous molecular sieve is provided, the acidity of the mesoporous molecular sieve can be improved, the catalytic activity of the mesoporous molecular sieve is improved, and the stability of the mesoporous molecular sieve is enhanced, so that the preparation method has important significance.
Disclosure of Invention
In order to solve the problems of weak acidity, low catalytic activity and weak stability of the mesoporous molecular sieve in the prior art, the invention provides a method for preparing an acidic mesoporous molecular sieve by using hydrogen peroxide.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing an acidic mesoporous molecular sieve by using hydrogen peroxide comprises the following steps:
(1.1) adding a CTAB surfactant into water, and stirring until the mixture is clear; preferably, the stirring time is 0.5-1 h, and the stirring temperature is 25-40 ℃;
(1.2) adding Na2SiO3·9H2Dissolving O in water, and stirring until the mixture is clear; preferably, the stirring time is 0.5-1 h, and the stirring temperature is 25-40 ℃;
(1.3) reacting H2O2Dissolving in water, performing primary irradiation with ultraviolet light at room temperature, and irradiating with the irradiated H2O2Dropwise addition of the solution to Na2SiO3In the solution, ultraviolet light is adopted again for irradiation; preferably, the time of the primary irradiation is 0.5 h; the time for re-irradiation of the ultraviolet light is 0.5-1 h;
(1.4) dropwise adding the solution obtained in the step (1.3) into a CTAB solution, stirring and mixing, then adjusting the pH of the solution by using hydrochloric acid, and continuously stirring at room temperature, preferably, adjusting the pH of the solution to 10.0-11.0;
(1.5) carrying out ultraviolet illumination on the initial molecular sieve gel obtained in the step (1.4) at room temperature to obtain a uniform gel system of the MCM-41 molecular sieve; preferably, the time of ultraviolet irradiation is 1-4 h;
(1.6) crystallizing, filtering, washing, drying and calcining the gel system to obtain an acidic mesoporous molecular sieve MCM-41; preferably, the drying time is 12-24h, and the drying temperature is 100-120 ℃; the calcination time is 8-10h, and the calcination temperature is 550-600 ℃.
The invention adds ultraviolet light and H in the preparation process of the mesoporous molecular sieve2O2The acidity of the mesoporous molecular sieve is improved, probably because the amount of hydroxyl radicals, H, in the system can be increased by ultraviolet irradiation2O2The active hydroxyl free radicals generate more silicon hydroxyl groups on the surface of the molecular sieve when the active hydroxyl free radicals are increased properly, so that the acidity of the product is improved; meanwhile, because metal heteroatoms are not introduced to modulate the acidity of the molecular sieve, no active component is introduced, the falling of the active component can not occur, and the stability of the molecular sieve is improved, thereby realizing the industrial production of the molecular sieve.
Meanwhile, the invention also provides an application of the acidic mesoporous molecular sieve in catalytic esterification reaction; the method can be applied to various esterification reactions, preferably, the invention takes the acidic mesoporous molecular sieve prepared by the preparation method as a catalyst, homoveratric acid and alcohol are subjected to esterification reaction to generate homoveratric ester, the type of the alcohol is not particularly limited, and preferably, common methanol or ethanol can be selected.
The esterification reaction is carried out in a high-pressure reaction kettle, magnetons are added in the reaction process, nitrogen is substituted for 3 times, the reaction is carried out for 4 hours at the temperature of 100 ℃, and centrifugation is carried out after the reaction is finished to collect supernatant fluid, so that the homoveratric ester is obtained.
Compared with the traditional hydrothermal method for preparing homoveratric acid ester, the acidic mesoporous molecular sieve MCM-41 prepared by the preparation method provided by the invention catalyzes homoveratric acid and alcohol to carry out esterification reaction, the conversion rate of homoveratric acid is greatly improved, and test results prove that in the preparation process of the molecular sieve provided by the invention, the conversion rate of homoveratric acid can reach more than 18%, and meanwhile, the prepared acidic mesoporous molecular sieve MCM-41 has stronger stability and can realize the industrial production of the molecular sieve.
Detailed Description
The invention discloses a method for preparing an acidic mesoporous molecular sieve by utilizing hydrogen peroxide and application of the acidic mesoporous molecular sieve, and a person skilled in the art can realize the preparation by properly improving process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
Example 1
3.2g CTAB surfactant in 20ml water at 40 deg.C under stirring for 1h to clear, 12.5g Na2SiO3·9H2O solution in 10ml of water at 40 ℃ for 1H until clear, then cooled to room temperature, 5ml of H2O2(30%) dissolved in 20ml deionized water, irradiated by ultraviolet light for 0.5H, and subjected to H2O2Slowly dripping the solution into sodium silicate solution, continuously irradiating for 0.5h, slowly dripping the mixed solution of hydrogen peroxide and sodium silicate into CTAB solution, mixing, stirring for 15min, adjusting pH to 10.5 with 2mol/L hydrochloric acid, continuously stirring at 25 deg.C for 3h, irradiating the obtained uniform gel under room temperature ultraviolet light for 3h, and transferring the obtained uniform gel to a medium-temperature ultraviolet lightAnd (3) transferring the obtained product to a polytetrafluoroethylene crystallization kettle for crystallization at 105 ℃, then performing suction filtration and washing by using deionized water, drying in a 105 ℃ oven for 24 hours, and finally calcining for 8 hours at 550 ℃ by using a muffle furnace to obtain the traditional hydrothermal method acidic molecular sieve MCM-41.
Example 2
1.6g CTAB surfactant in 20ml water at 25 deg.C for 05h stirring to clear, 12.5g Na2SiO3·9H2Dissolving O in 10ml of water, stirring for 0.5h at 25 ℃ until the solution is clear, and then cooling to room temperature; 5ml of H2O2(30%) dissolved in 20ml deionized water and irradiated by ultraviolet light for 0.5H2O2Slowly dropping the solution into a sodium silicate solution, continuously illuminating for 1h, slowly dropping a mixed solution of hydrogen peroxide and sodium silicate into a CTAB solution, mixing for 15min, adjusting the pH to 10 by using 2mol/L hydrochloric acid, continuously stirring for 3h at 25 ℃, irradiating the obtained uniform gel for 1h under room temperature ultraviolet light, transferring the obtained uniform gel into a polytetrafluoroethylene crystallization kettle, crystallizing at 105 ℃, performing suction filtration and washing by using deionized water, drying for 24h in a 100 ℃ oven, and finally calcining for 8h at 550 ℃ by using a muffle furnace to obtain the acidic molecular sieve MCM-41.
Example 3
3.2g CTAB surfactant in 20ml water at 40 deg.C under stirring for 1h to clear, 12.5g Na2SiO3·9H2Dissolving O in 10ml of water, stirring at 40 ℃ until the solution is clear, and then cooling to room temperature; 5ml of H2O2(30%) dissolved in 20ml deionized water and irradiated by ultraviolet light for 0.5H2O2Slowly dropping the solution into a sodium silicate solution, continuously illuminating for 0.8h, slowly dropping a mixed solution of hydrogen peroxide and sodium silicate into a CTAB solution, mixing for 15min, adjusting the pH to 11 with 2mol/L hydrochloric acid, continuously stirring for 3h at 25 ℃, irradiating the obtained uniform gel for 4h under room temperature ultraviolet light, transferring the obtained uniform gel into a polytetrafluoroethylene crystallization kettle, crystallizing at 105 ℃, performing suction filtration and washing with deionized water, drying in a drying oven at 110 ℃ for 18h, and finally calcining for 9h at 580 ℃ in a muffle furnace to obtain the acid molecular sieve MCM-41.
Example 5
Weighing 2g (0.01mol) homoveratric acid, weighing a certain amount of methanol (0.3mol) and adding into a 75ml high-pressure reaction kettle, adding acidic molecular sieve MCM-410.05g prepared in example 1, adding magnetons, and replacing with nitrogen for 3 times. Introducing 2.5Mpa nitrogen, rotating at 630/min, reacting at 100 deg.C for 4 hr, centrifuging the reaction product to remove supernatant to obtain homoveratric ester; homoveratric acid conversion was 18.56% when the reactant was methanol and 21.66% when the reactant was ethanol.
Comparative example 1
3.2g CTAB surfactant in 20ml water at 40 deg.C under stirring for 1h to clear, 12.5g Na2SiO3·9H2Dissolving O in 10ml of water, and stirring at 40 ℃ until the solution is clear; and cooling the two solutions to room temperature, slowly dropwise adding the sodium silicate solution into the CTAB solution, mixing, and stirring for 15 min. And then adjusting the pH value to 10.5 by using 2mol/L hydrochloric acid, continuously stirring for 3 hours at 25 ℃, transferring the obtained uniform gel into a polytetrafluoroethylene crystallization kettle, crystallizing at 105 ℃, then performing suction filtration and washing by using deionized water, drying for 24 hours in a 105 ℃ oven, and finally calcining for 8 hours at 550 ℃ by using a muffle furnace to obtain the traditional hydrothermal acidic molecular sieve MCM-41.
Weighing 2g (0.01mol) homoveratric acid, weighing a certain amount of alcohol (0.3mol), adding into a 75ml high-pressure reaction kettle, adding into MCM-410.05g of the traditional hydrothermal molecular sieve of the comparative example 1, adding magnetons, replacing with nitrogen for 3 times, charging 2.5Mpa nitrogen, rotating at the speed of 630/min, reacting at 100 ℃ for 4h, centrifuging the reaction product, collecting the supernatant to obtain homoveratric ester, and taking a comparison group, wherein the homoveratric acid conversion rate is 8.28% when the reactant is methanol, and 12.53% when the reactant is ethanol.
Comparative example 2
Weighing 2g (0.01mol) homoveratric acid, measuring a certain amount of alcohol (0.3mol), adding into a 75ml high-pressure reaction kettle, placing magneton, replacing with nitrogen for 3 times, charging 2.5Mpa nitrogen, rotating at 630/min, reacting at 100 ℃ for 4h, centrifuging the reaction product, collecting the supernatant to obtain homoveratric ester, and making blank group, wherein the homoveratric acid conversion rate is 5.05% when the reactant is methanol, and 3.05% when the reactant is ethanol.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing an acidic mesoporous molecular sieve by using hydrogen peroxide is characterized by comprising the following steps:
(1.1) adding a CTAB surfactant into water, and stirring until the mixture is clear;
(1.2) adding Na2SiO3·9H2Dissolving O in water, and stirring until the mixture is clear;
(1.3) reacting H2O2Dissolving in water, performing primary irradiation with ultraviolet light at room temperature, and irradiating with the irradiated H2O2Dropwise addition of the solution to Na2SiO3In the solution, ultraviolet light is adopted again for irradiation;
(1.4) dropwise adding the solution obtained in the step (1.3) into a CTAB solution, stirring and mixing, adjusting the pH value of the solution by using hydrochloric acid, and continuously stirring at room temperature;
(1.5) carrying out ultraviolet illumination on the initial molecular sieve gel obtained in the step (1.4) at room temperature to obtain a uniform gel system of the MCM-41 molecular sieve;
and (1.6) crystallizing, filtering, washing, drying and calcining the gel system to obtain the acidic mesoporous molecular sieve MCM-41.
2. The method of claim 1, wherein the stirring time of step (1.1) is 0.5 to 1 hour, and the stirring temperature is 25 to 40 ℃.
3. The method of claim 1, wherein the stirring time in step (1.2) is 0.5 to 1 hour, and the stirring temperature is 25 to 40 ℃.
4. The method of claim 1, wherein the time for the first irradiation of the ultraviolet light in the step (1.3) is 0.5h, and the time for the second irradiation of the ultraviolet light is 0.5 to 1 h.
5. The method according to claim 1, wherein in step (1.4), the hydrochloric acid adjusts the pH of the solution to 10.0 to 11.0.
6. The method of claim 1, wherein in step (1.5), the ultraviolet light is applied for 1-4 hours.
7. The method according to claim 1, wherein in the step (1.6), the drying time is 12-24 hours, and the drying temperature is 100-120 ℃; the calcining time is 8-10h, and the calcining temperature is 550-600 ℃.
8. Use of the acidic mesoporous molecular sieve prepared by the method of any of claims 1 to 7 in catalytic esterification reactions.
9. The use of claim 8, wherein said esterification reaction of homoveratric acid and alcohol is carried out in the presence of the acidic mesoporous molecular sieve of claim 8 as a catalyst to form homoveratric esters.
10. The use of claim 9, wherein the esterification reaction is carried out in a high pressure reactor, magnetons are added during the reaction, nitrogen is used for replacement for 3 times, the reaction is carried out for 4 hours at 100 ℃, and after the reaction is finished, the supernatant is collected by centrifugation to obtain the homoveratric ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810945900.1A CN109126860B (en) | 2018-08-20 | 2018-08-20 | Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810945900.1A CN109126860B (en) | 2018-08-20 | 2018-08-20 | Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109126860A CN109126860A (en) | 2019-01-04 |
| CN109126860B true CN109126860B (en) | 2021-09-10 |
Family
ID=64790166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810945900.1A Active CN109126860B (en) | 2018-08-20 | 2018-08-20 | Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109126860B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126860B (en) * | 2018-08-20 | 2021-09-10 | 青岛科技大学 | Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve |
| CN114477221B (en) * | 2021-12-30 | 2023-08-11 | 天津大学 | ZK-5 molecular sieve and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877762A (en) * | 2015-05-09 | 2015-09-02 | 青岛科技大学 | Method for catalyzing esterification reaction by means of high-stable-acidity mesoporous-microporous molecular sieve |
| CN104891463A (en) * | 2014-03-05 | 2015-09-09 | 哈尔滨商业大学 | Preparation and applications of composite SBA-15 molecular sieve catalysts |
| CN106829993A (en) * | 2017-02-09 | 2017-06-13 | 吉林大学 | A kind of method that the mesopore molecular sieves of green syt SBA 15 are aided in by ultraviolet radiation |
| CN107188194A (en) * | 2017-05-04 | 2017-09-22 | 郑州大学 | A kind of method for preparing high catalytic activity Ti MWW molecular sieves |
| CN109126860A (en) * | 2018-08-20 | 2019-01-04 | 青岛科技大学 | A kind of application for the method and acid mesopore molecular sieve preparing acid mesopore molecular sieve using hydrogen peroxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9636669B2 (en) * | 2013-02-22 | 2017-05-02 | The Regents Of The University Of California | Zeolitic materials with heteroatom substitutions on external surface of lattice framework |
-
2018
- 2018-08-20 CN CN201810945900.1A patent/CN109126860B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891463A (en) * | 2014-03-05 | 2015-09-09 | 哈尔滨商业大学 | Preparation and applications of composite SBA-15 molecular sieve catalysts |
| CN104877762A (en) * | 2015-05-09 | 2015-09-02 | 青岛科技大学 | Method for catalyzing esterification reaction by means of high-stable-acidity mesoporous-microporous molecular sieve |
| CN106829993A (en) * | 2017-02-09 | 2017-06-13 | 吉林大学 | A kind of method that the mesopore molecular sieves of green syt SBA 15 are aided in by ultraviolet radiation |
| CN107188194A (en) * | 2017-05-04 | 2017-09-22 | 郑州大学 | A kind of method for preparing high catalytic activity Ti MWW molecular sieves |
| CN109126860A (en) * | 2018-08-20 | 2019-01-04 | 青岛科技大学 | A kind of application for the method and acid mesopore molecular sieve preparing acid mesopore molecular sieve using hydrogen peroxide |
Non-Patent Citations (3)
| Title |
|---|
| "MCM-41催化合成丙烯酸高级醇酯";吕亮等;《皮革化工》;20010825;第18卷(第4期);摘要以及第31页右栏第3段 * |
| "纯硅MCM-41的制备及表征";龚德志等;《科学发展与社会责任（A卷）-第五届沈阳科学学术年会论文集》;20081031;第250页第5段 * |
| "通过不同方法生产羟基自由基加速沸石分子筛的合成的研究";程鹏;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20160815(第8期);第37页第2段-第38页第1段、第47页第2段、第49页第3段、第50页第1段-第51页第1段以及第69页第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109126860A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109126860B (en) | Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve | |
| JP2022506869A (en) | Method for manufacturing TS-1 molecular sieve having hierarchical pores | |
| CN111170982B (en) | Method for improving selectivity of cyclohexanone oxidation reaction product epsilon-caprolactone | |
| CN108285152B (en) | Green and efficient synthesis method of copper-doped SBA-15 mesoporous molecular sieve material | |
| CN101264892A (en) | Method for preparing double-channel mesoporous silicon oxide hollow sphere | |
| CN114438072B (en) | Production method of trehalose | |
| CN109248707B (en) | Preparation method of acidic mesoporous molecular sieve and application of acidic mesoporous molecular sieve in catalytic esterification reaction | |
| CN103769205B (en) | A kind of preparation method of the composite catalyst for oil-containing micro-algae hydrothermal liquefaction | |
| CN109225314B (en) | Method for preparing acidic mesoporous molecular sieve by using sodium persulfate and application of acidic mesoporous molecular sieve | |
| CN101857267A (en) | Preparation method of titanium dioxide nano material with core-shell structure | |
| CN113181967A (en) | Application of titanium sulfonate modified KIT-6 solid acid catalyst in borneol synthesis | |
| CN108285174B (en) | WO (WO)3-ZrO2Preparation method of photocatalytic sewage treatment membrane | |
| CN109746004B (en) | Catalyst and application thereof in preparation of 2,2,6, 6-tetramethyl-4-piperidone | |
| CN104525183B (en) | A kind of mesoporous catalyst loading chromio and its preparation method and application | |
| CN108940366B (en) | Preparation method of pore-adjustable Fe-based metal organic framework-phosphotungstic acid | |
| CN110407220A (en) | A kind of fast preparation method of bigger serface SAPO-34 molecular sieve | |
| CN108404917A (en) | A kind of preparation method of NiTiO3-ZrO2 sewage disposals film | |
| CN109850890A (en) | A kind of preparation of Activated Carbon For Desulphurization From Furfural Residue base iron zincic acid desulfurizing agent | |
| CN112979406A (en) | Method for catalyzing alpha-pinene dimerization-hydrogenation reaction by using bifunctional microporous molecular sieve | |
| CN111392744A (en) | Preparation method of hierarchical porous Fe-MFI molecular sieve | |
| Zhiani et al. | Phosphosilicate nanosheets for supported palladium nanoparticles as a novel nanocatalyst | |
| CN115784252B (en) | Preparation method of mesoporous ZSM-5 molecular sieve | |
| CN114702384B (en) | Method for preparing p-hydroxy cinnamic acid ester by catalyzing alcoholysis of lignin through enzymolysis lignin-based hierarchical porous carbon loaded molybdenum oxide | |
| CN112536060A (en) | Catalyst for preparing dimer acid, dimer acid and preparation method and application thereof | |
| CN110436479A (en) | A kind of Titanium Sieve Molecular Sieve and its preparation method and application |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 266061 Songling Road, Laoshan District, Qingdao, Shandong Province, No. 99 Patentee after: QINGDAO University OF SCIENCE AND TECHNOLOGY Address before: 266042 Zhengzhou Road, Shibei District, Qingdao, Shandong 53 Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY |
|
| CP02 | Change in the address of a patent holder |