CN103920527A - Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof - Google Patents
Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103920527A CN103920527A CN201410169234.9A CN201410169234A CN103920527A CN 103920527 A CN103920527 A CN 103920527A CN 201410169234 A CN201410169234 A CN 201410169234A CN 103920527 A CN103920527 A CN 103920527A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- glycol
- acid treatment
- epoxide
- preparation
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing a 1,2-glycol by epoxy compound through hydration as well as a preparation method and an application thereof. A beta zeolite molecular sieve is used as a raw material and then is subjected to acid treatment, and active centered metal is introduced through roasting; and the preparation method comprises the steps of mixing the beta zeolite molecular sieve after acid treatment with an organometallic compound precursor according to the proportion, and roasting. The method can solve the problems of high water ratio, high energy consumption and environment pollution caused by a production process in the traditional process; and the catalyst carrier is cheap and easily available, the preparation process of the catalyst is simple and has good stability, and the catalyst has excellent catalytic activity and the good selectivity in the glycol preparation process by the epoxy compound under a mild condition, and can be applied to glycol industrial production through epoxy compound hydration.
Description
Technical field
The present invention relates to a kind of epoxide hydration and prepare catalyst and the preparation method and application of 1,2-glycol, is specifically catalyst and the application process that raw material direct hydration is prepared 1,2-glycol with epoxide.
Background technology
1,2-glycol, as important Organic Chemicals, is mainly used in synthesizing polyester resin, antifreezing agent, cosmetics, photographic material, lubricant, medicine intermediate and multiple fine chemicals etc.Industrial, it is to have one of process route of application prospect most that direct catalysis hydration epoxide is prepared 1,2-glycol synthetic method.Therefore, in recent years, develop the focus that efficient water-fast catalyst is this research direction always, the difficult problem that Ye Shi lot of domestic and foreign scientific research institution and enterprise need to be captured.
In recent decades, for the catalyst series of this reaction of catalysis and Patents technology, Bei Ge great research institution and company develop in succession, wherein most of exploitation mainly concentrates on various solid/liquid class acid base catalysators, comprises the resin, the macromolecule organic silicon alkanamine of sulfuric acid, ring-type organic amine, cation or anion exchange, encircles chelate compound and load metal oxide greatly.Although correlation technique has obtained higher glycol yield, also inevitably face some technological deficiencies simultaneously: as serious in easily caused equipment corrosion in production process, cause production hidden danger; For fear of part diol product in production process dimerization or trimerization and form a large amount of accessory substances under the effect of catalyst, thereby adopt the inventory (mol ratio of water and epoxide is greater than 20) that adds flood to reach the object of dilution.Although this measure has effectively suppressed the formation of by-product, subsequent purification process has consumed a large amount of energy, causes production cost significantly to promote.
Summary of the invention
The object of this invention is to provide a kind of epoxide hydration and prepare catalyst and the preparation method and application of 1,2-glycol.The present invention can solve the problem such as high water ratio, high energy consumption and environmental pollution in traditional glycol preparation technology, this catalyst has stronger acid and excellent stability, at epoxide direct hydration, prepare in the reaction of glycol, approach room temperature (40 ℃) and low water can catalysis for example, than the condition of (mol ratio of water and epoxide is 2) under obtain excellent catalytic activity and glycol selective.
Provided by the inventionly for epoxide direct hydration, prepare 1, the catalyst of 2-glycol is that to take business-like Beta zeolite molecular sieve be raw material, through acid treatment with introduce activated centre metal by roasting and make, preparation method is, by metering, the Beta zeolite molecular sieve after acid treatment is mixed to roasting with organo-metallic compound presoma.
Described content of metal is the 1-5% of catalyst quality; Described metal is tin, zirconium or titanium; Described acid treatment is red fuming nitric acid (RFNA), hydrochloric acid or oxalic acid treatment; Described organo-metallic compound presoma is dimethyltin chloride, bicyclic pentadiene zirconium dichloride or dicyclic pentylene titanium dichloride;
Described epoxide is 7-oxa-bicyclo[4.1.0, oxirane, expoxy propane, epoxychloropropane, epoxy butane and Styryl oxide; Described 1,2-glycol is 1,2-cyclohexanediol, ethylene glycol, 1,2-PD, 3-chlorine-1,2-propylene glycol, 1,2-butanediol and styrene glycol.
The preparation method who prepares the catalyst of 1,2-glycol for epoxide direct hydration provided by the invention comprises the steps:
1) by Beta molecular screen primary powder (mol ratio: SiO
2/ Al
2o
3=25-100) under the condition of concentrated acid (red fuming nitric acid (RFNA), concentrated hydrochloric acid or oxalic acid solution), process, treatment temperature is 25-150 ℃, processing time 1-40h;
2) catalyst mixture after acid treatment is carried out to decompress filter, the filter cake obtaining is washed to after neutrality, constant temperature 12-24 hour in air dry oven, and temperature is 80-120 ℃;
3) mix in grinding with organo-metallic compound presoma, then mixture is placed in to Muffle furnace roasting, sintering temperature is 350-650 ℃, and roasting time is 6-12h;
The application process of preparing the catalyst of glycol for epoxide direct hydration provided by the invention comprises the steps:
1) catalyst, epoxide and water are placed in to pressure reaction still, airtight, with nitrogen purge reactor, discharge the air in reactor, then to squeezing into nitrogen in reactor, maintain 1.0Mpa pressure;
2) pressure reaction still is placed in to stirring reaction on preheated reactor, can makes product.Reaction condition is 40-80 ℃, and the reaction time is 4-6h.
3) product gas chromatographic analysis.
The mol ratio of epoxide and water is 1: 1-10, and stir speed (S.S.) is 800 revs/min;
The rate of charge of described catalyst and epoxide is 1: 100 (g/mmol).
Acidity of catalyst of the present invention is stronger, can directly apply, preparation process is simple to operation, structural behaviour is stable, catalyst can be for reacting at epoxide catalysis hydration glycol processed under the temperate condition that approaches room temperature and low water ratio, and show excellent catalytic activity and higher glycol selective, after reaction finishes, only by roasting, just can repeatedly recycle, catalytic activity is without obvious decline; This catalyst preparation process is simple, and with low cost, and Catalytic processes is environment friendly and pollution-free, can prepare large-scale promotion application in the reaction of glycol in epoxide hydration.
Accompanying drawing explanation
Fig. 1 is the SEM figure of prepared catalyst.
Fig. 2 is the XRD figure of prepared molecular sieve catalyst.
Fig. 3 is the UV-vis figure of prepared catalyst.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is done to further detailed, complete explanation.
In following embodiment, related specific experiment method and apparatus if no special instructions, is conventional method or implements according to the condition of manufacturer's description suggestion.Related reagent is commercially available.Beta molecular screen primary powder of the present invention is purchased from Shenneng Science-Technology Co., Ltd., Tianjin, silica alumina ratio (SiO
2/ Al
2o
3) be 25-100.
Embodiment 1:
In the present embodiment, the preparation process of 4%Sn-Beta catalyst used comprises the steps:
1) by a certain amount of Beta molecular screen primary powder (SiO
2/ A
2o
3=25) be placed in there-necked flask with red fuming nitric acid (RFNA), concentrated hydrochloric acid or oxalic acid solution and mix, in the oil bath reactor of 100 ℃, heat return stirring 20h.Wherein, the rate of charge of Beta molecular screen primary powder and acid solution is 1: 20 (g/mL);
2) after the solidliquid mixture after return stirring is fully cooling, add wherein deionized water to be diluted to certain concentration, after decompress filter, by the filter cake of gained with the washing of a large amount of deionized water to neutral, be then placed on freeze-day with constant temperature 12h in the air dry oven of 100 ℃;
3) in glove box, take step 2) in the dimethyltin chloride organic precursor of a certain amount of pressed powder and aequum, after grinding fully with agate mortar, be placed in Muffle furnace high-temperature roasting and obtain required catalyst.Wherein, sintering temperature is 550 ℃, and roasting time is 6h.
For convenient below statement, by the molecular sieve difference called after 4%Sn-Beta-X, 4%Sn-Beta-Y and the 4%Sn-Beta-C that process through nitric acid, hydrochloric acid and oxalic acid solution.
4%Sn-Beta catalyst is prepared to 1,2-cyclohexanediol for different water than 7-oxa-bicyclo[4.1.0 hydration under condition to be comprised the steps:
1) by the 4%Sn-Beta catalyst of 0.1g, the 7-oxa-bicyclo[4.1.0 of 10mmol and water drop in the liner of polytetrafluoroethylene (PTFE) material of pressure reactor, and sealed reactor, rinses reactor three times with high pure nitrogen, maintain in reactor pressure at 1.0Mpa;
2) pressure reactor is placed on preheated reactor, adds after thermal agitation a period of time, can make product.Catalytic reaction condition is: reaction temperature is 40 ℃, and the reaction time is 6h, and the mol ratio of epoxide and water is 1: 2, and stir speed (S.S.) is 800 revs/min;
3) product gas chromatographic analysis.Gas-chromatography used is Shimadzu 2010 gas chromatographs, collocation fid detector, and capillary chromatograph model is Agilent HP-5MS.Adopt temperature programming to carry out separation to product, heating step is as follows: initial temperature is 80 ℃, insulation 3min, and then the speed with 15 ℃/min is warming up to 250 ℃, insulation 5min.By chromatographic work station, utilize internal standard method to ask to calculate the selective of the conversion ratio of raw material and target product.Catalytic performance test the results are shown in Table 1:
The impact of hexylene glycol technique is changed in the different acid treatments of table 1 on 7-oxa-bicyclo[4.1.0 hydration preparation
Catalytic performance test result shows: the sample after dissimilar acid treatment, the obvious difference of selective existence of the conversion ratio of its 7-oxa-bicyclo[4.1.0 under same reaction conditions and cyclohexanediol.Catalyst sample through nitric acid treatment shows the most excellent catalytic activity in the reaction of catalysis 7-oxa-bicyclo[4.1.0 hydration, and the productive rate of glycol is up to 83.6%.
Embodiment 2:
It is nitric acid that the present embodiment is processed molecular screen primary powder acid used, has investigated under 100 ℃ for the treatment of temperatures, and nitric acid treatment different time sections is the impact on catalysis 7-oxa-bicyclo[4.1.0 hydration performance on 4%Sn-Beta catalyst, and catalytic performance test is in Table 2:
Table 2 nitric acid treatment different time sections on 7-oxa-bicyclo[4.1.0 hydration prepare the impact of cyclohexanediol technique
Catalytic performance test result shows: along with the increase of nitric acid treatment time, selectively all being improved accordingly of the conversion ratio of 7-oxa-bicyclo[4.1.0 and target product, when the acid treatment time, reach 20h, the productive rate of glycol is 83.6% to the maximum, continue to extend the acid treatment time, to reaction effect without obvious facilitation.
Embodiment 3:
The present embodiment is investigated the impact of different organometallic precursors on catalysis 7-oxa-bicyclo[4.1.0 hydration performance, and other reaction conditions are with described in embodiment 2.Catalytic performance test the results are shown in Table 3:
The different organometallic precursors of table 3 on 7-oxa-bicyclo[4.1.0 hydration prepare the impact of cyclohexanediol technique
Catalytic performance test result shows: different catalytic active centers shows obvious difference to reacting catalytic performance, compare bicyclic pentadiene zirconium dichloride and dicyclic pentylene titanium dichloride, the 4%Sn-Beta catalyst being made by dimethyltin chloride roasting is active best, also shows excellent catalytic selectivity simultaneously.
Implementation column 4:
The impact of the percentage composition that the present embodiment object is to investigate tin on catalysis 7-oxa-bicyclo[4.1.0 hydration performance, other reaction conditions are with described in embodiment 3.Catalytic performance test the results are shown in Table 4:
Table 4 different tin content on 7-oxa-bicyclo[4.1.0 hydration prepare the impact of cyclohexanediol technique
Catalytic performance test result shows: in catalyst, tin content also has obvious impact to catalytic performance.When tin content is increased to 4% from 2%, the conversion ratio of 7-oxa-bicyclo[4.1.0 obviously increases, and reaches 90.2mol%, and when continuing to increase tin content to 5%, conversion ratio and the cyclohexanediol of 7-oxa-bicyclo[4.1.0 selectively do not rise appreciably.
Embodiment 5:
The present embodiment has been investigated different water than under condition, the impact of 4%Sn-Beta catalyst on catalysis 7-oxa-bicyclo[4.1.0 hydration performance, and other reaction conditions are with described in embodiment 4.Catalytic performance test the results are shown in Table 5:
The impact of cyclohexanediol technique is prepared in the hydration of the different water comparison of table 5 7-oxa-bicyclo[4.1.0
Catalytic performance test result shows: along with the increase of water inventory, the conversion ratio of 7-oxa-bicyclo[4.1.0 also increases thereupon, and the selective raising of glycol is not obvious.Meanwhile, after the water yield increases, given prominence to the later stage except water extracting alcohol glycol process energy consumption problem, therefore considered, when the mol ratio of water and 7-oxa-bicyclo[4.1.0 is 2: 1, the productive rate of glycol reaches 83.6%, is desirable process conditions.
Embodiment 6:
The present embodiment has been investigated under optimum reaction condition, and 4%Sn-Beta catalyst is applied to the effect that recycles in catalysis 7-oxa-bicyclo[4.1.0 hydration reaction.Catalyst every through once circulation after, in Muffle furnace after roasting for next time reaction.Reaction condition is: reaction temperature is 40 ℃, and the reaction time is 6h, and the mol ratio of water and 7-oxa-bicyclo[4.1.0 is 2: 1, N
2pressure is 1.0Mpa, and stir speed (S.S.) is 800 turn/min, and sintering temperature is 550 ℃.Catalyst circulation is used and be the results are shown in Table 6:
Table 6 catalyst circulation result of use
Catalytic performance test result shows: under optimum reaction condition, catalyst its catalytic performance after at least 5 times recycle does not decline.
Embodiment 7:
The present embodiment has been investigated the catalytic performance of other epoxy substrates of 4%Sn-Beta catalyst, and reaction temperature is 40 ℃, and the mol ratio of water and epoxide is 2: 1.
The catalytic effect of table 7 catalyst to different epoxy substrates
Catalytic performance test result shows: this catalyst applied widely, under the condition of lower temperature and low water ratio, the conversion ratio of various epoxy substrates and glycol are selectively all higher.
Claims (10)
1. one kind for epoxide direct hydration system 1, the catalyst of 2-glycol, it is characterized in that it is to take Beta zeolite molecular sieve as raw material, through acid treatment with introduce activated centre metal by roasting and make, preparation method is, by metering, the Beta zeolite molecular sieve after acid treatment is mixed to roasting with organo-metallic compound presoma; Described content of metal is the 1-5% of catalyst quality; Described metal is tin, zirconium or titanium.
2. catalyst according to claim 1, is characterized in that described acid treatment is red fuming nitric acid (RFNA), hydrochloric acid or oxalic acid treatment.
3. catalyst according to claim 1, is characterized in that described organo-metallic compound presoma is dimethyltin chloride, bicyclic pentadiene zirconium dichloride or dicyclic pentylene titanium dichloride.
4. catalyst according to claim 1, is characterized in that described epoxide is 7-oxa-bicyclo[4.1.0, oxirane, expoxy propane, epoxychloropropane, epoxy butane and bad oxygen vinylbenzene.
5. catalyst according to claim 1, is characterized in that describedly 1, and 2-glycol is 1,2-cyclohexanediol, ethylene glycol, 1,2-PD, 3-chlorine-1,2-propylene glycol, 1,2-butanediol and styrene glycol.
6. an epoxide direct hydration claimed in claim 1 is prepared the preparation method of the catalyst of 1,2-glycol, it is characterized in that comprising the steps:
1) Beta molecular screen primary powder is processed under the condition of concentrated acid, treatment temperature is 25-150 ℃, processing time 1-40h; SiO
2/ Al
2o
3=25-100;
2) catalyst mixture after acid treatment is carried out to decompress filter, the filter cake obtaining is washed to after neutrality, constant temperature 12-24 hour very in air dry oven, and temperature is 80-120 ℃;
3) mix in grinding with organo-metallic compound presoma, then mixture is placed in to Muffle furnace roasting, sintering temperature is 350-650 ℃, and roasting time is 6-12h.
7. method according to claim 6, is characterized in that described acid treatment is red fuming nitric acid (RFNA), hydrochloric acid or oxalic acid treatment.
8. method according to claim 6, is characterized in that described organo-metallic compound presoma is dimethyltin chloride, bicyclic pentadiene zirconium dichloride or dicyclic pentylene titanium dichloride.
9. method according to claim 6, is characterized in that described SiO
2/ A
2o
3=25.
10. the application process of the arbitrary catalyst described in claim 1-5, is characterized in that comprising the steps:
1) catalyst, epoxide and water are placed in to pressure reaction still, airtight, with nitrogen purge reactor, discharge the air in reactor, then to squeezing into nitrogen in reactor, maintain 1.0Mpa pressure;
2) pressure reaction still is placed in to stirring reaction on preheated reactor, can makes product; Reaction condition is 40-80 ℃, and the reaction time is 4-6h;
3) product gas chromatographic analysis;
The mol ratio of epoxide and water is 1: 1-10, stir speed (S.S.) is 800 revs/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410169234.9A CN103920527B (en) | 2014-04-24 | 2014-04-24 | Catalyst and the preparation method and application of 1,2-glycol are prepared in epoxide hydration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410169234.9A CN103920527B (en) | 2014-04-24 | 2014-04-24 | Catalyst and the preparation method and application of 1,2-glycol are prepared in epoxide hydration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103920527A true CN103920527A (en) | 2014-07-16 |
| CN103920527B CN103920527B (en) | 2016-01-13 |
Family
ID=51139060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410169234.9A Expired - Fee Related CN103920527B (en) | 2014-04-24 | 2014-04-24 | Catalyst and the preparation method and application of 1,2-glycol are prepared in epoxide hydration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103920527B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437607A (en) * | 2014-11-06 | 2015-03-25 | 南开大学 | Tin-containing molecular sieve catalyst used for preparing ethylene glycol by hydrating ethylene oxide and application method |
| CN104892365A (en) * | 2015-05-27 | 2015-09-09 | 泰山医学院 | Method for synthesizing high-purity glycerin chlorohydrin under low pressure |
| CN106824259A (en) * | 2016-12-21 | 2017-06-13 | 南开大学 | For the method for preparation and use of the catalyst of ethanol conversion 1,3 butadiene of system |
| CN108097300A (en) * | 2017-12-15 | 2018-06-01 | 南开大学 | Catalyst for preparing isobutene for acetic acid conversion and preparation method thereof |
| CN108129260A (en) * | 2017-12-21 | 2018-06-08 | 常州南京大学高新技术研究院 | A kind of synthetic method of styrene glycol |
| CN108855207A (en) * | 2018-06-17 | 2018-11-23 | 复旦大学 | Hetero atom Beta zeolite catalyst of alkali metal containing and its preparation method and application |
| CN110354899A (en) * | 2019-08-22 | 2019-10-22 | 华东师范大学 | A kind of solid acid catalyst and preparation method and the application in epoxide hydration |
| CN111939975A (en) * | 2020-08-24 | 2020-11-17 | 南开大学 | Bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin and application thereof |
| CN115722259A (en) * | 2021-08-26 | 2023-03-03 | 中国科学院广州能源研究所 | Synthetic method of space-adjacent bimetallic heteroatom molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0943594B1 (en) * | 1998-02-24 | 2003-04-09 | Fina Technology, Inc. | Aromatic alkylation process |
| CN102039171A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Preparation method of non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst |
-
2014
- 2014-04-24 CN CN201410169234.9A patent/CN103920527B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0943594B1 (en) * | 1998-02-24 | 2003-04-09 | Fina Technology, Inc. | Aromatic alkylation process |
| CN102039171A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Preparation method of non-binder ZSM-5/zeolite beta coexisting molecular sieve catalyst |
Non-Patent Citations (1)
| Title |
|---|
| BO TANG等: "A procedure for the preparation of Ti-Beta zeolites for catalytic epoxidation with hydrogen peroxide", 《GREEN CHEM.》, vol. 16, 20 January 2014 (2014-01-20) * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437607A (en) * | 2014-11-06 | 2015-03-25 | 南开大学 | Tin-containing molecular sieve catalyst used for preparing ethylene glycol by hydrating ethylene oxide and application method |
| CN104892365A (en) * | 2015-05-27 | 2015-09-09 | 泰山医学院 | Method for synthesizing high-purity glycerin chlorohydrin under low pressure |
| CN106824259B (en) * | 2016-12-21 | 2019-07-12 | 南开大学 | The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion |
| CN106824259A (en) * | 2016-12-21 | 2017-06-13 | 南开大学 | For the method for preparation and use of the catalyst of ethanol conversion 1,3 butadiene of system |
| CN108097300A (en) * | 2017-12-15 | 2018-06-01 | 南开大学 | Catalyst for preparing isobutene for acetic acid conversion and preparation method thereof |
| CN108097300B (en) * | 2017-12-15 | 2020-06-05 | 南开大学 | Catalyst for preparing isobutene by acetic acid conversion and preparation method thereof |
| CN108129260A (en) * | 2017-12-21 | 2018-06-08 | 常州南京大学高新技术研究院 | A kind of synthetic method of styrene glycol |
| CN108855207A (en) * | 2018-06-17 | 2018-11-23 | 复旦大学 | Hetero atom Beta zeolite catalyst of alkali metal containing and its preparation method and application |
| CN108855207B (en) * | 2018-06-17 | 2021-04-27 | 复旦大学 | Heteroatom Beta zeolite catalyst containing alkali metal and preparation method and application thereof |
| CN110354899A (en) * | 2019-08-22 | 2019-10-22 | 华东师范大学 | A kind of solid acid catalyst and preparation method and the application in epoxide hydration |
| CN111939975A (en) * | 2020-08-24 | 2020-11-17 | 南开大学 | Bifunctional molecular sieve catalyst for directly preparing 1, 2-diol by catalyzing olefin and application thereof |
| CN111939975B (en) * | 2020-08-24 | 2023-03-28 | 南开大学 | Bifunctional molecular sieve catalyst for directly preparing 1,2-diol by catalyzing olefin and application thereof |
| CN115722259A (en) * | 2021-08-26 | 2023-03-03 | 中国科学院广州能源研究所 | Synthetic method of space-adjacent bimetallic heteroatom molecular sieve |
| CN115722259B (en) * | 2021-08-26 | 2024-02-09 | 中国科学院广州能源研究所 | Synthesis method of space adjacent bimetallic heteroatom molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103920527B (en) | 2016-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103920527B (en) | Catalyst and the preparation method and application of 1,2-glycol are prepared in epoxide hydration | |
| CN109675602B (en) | Supported cobalt-nitrogen doped carbon catalyst and preparation method and application thereof | |
| CN103721738B (en) | A kind of non-metal optical catalysis material of efficient reducing carbon dioxide | |
| CN103570493A (en) | Method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation | |
| CN102600860A (en) | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof | |
| CN106732768A (en) | A kind of solid-carrying type ionic-liquid catalyst for carbon dioxide cycloaddition reaction and preparation method thereof | |
| CN105413740A (en) | High-efficiency Fe-SCR integrated catalyst preparation method | |
| CN103143381B (en) | Carbon-nitrogen material immobilized heteropoly acid catalyst and olefin epoxidation synthesis method | |
| CN103664656A (en) | Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid | |
| CN103537314B (en) | A kind of preparing acetaldehyde by ethane selective oxidation and ethene catalyst and Synthesis and applications | |
| CN105344351A (en) | Preparation method and application of nitric acid-assisting oxygen-vacancy-adjustable LaMnO3 | |
| CN104383965A (en) | Metal-organic framework immobilized tungsten oxide catalyst for synthesizing glutaraldehyde and production method of metal-organic framework immobilized tungsten oxide catalyst | |
| CN101838197A (en) | Method for preparing 2,2,4-trimethyl-1,3-pentanediol single-isobutyrate | |
| CN105732520A (en) | Method of synthesizing quinazolinone-structured compound | |
| CN104437607B (en) | Stanniferous molecular sieve catalyst and the using method of ethylene glycol is prepared for ethylene oxide hydration | |
| CN104495957A (en) | Preparation method of doped poly(nickel aluminophosphate) hydrotalcite | |
| CN104588025B (en) | A kind of self assembly near-spherical Sm2o3the preparation method of/CuO nano-complex | |
| CN107866224A (en) | Catalyst and its production and use | |
| CN109529906B (en) | Catalyst for synthesizing 1,1,2,3,3, 3-hexafluoropropyl methyl ether and preparation method thereof | |
| CN103801393A (en) | Preparation method of catalyst for phenol preparation by benzene hydroxylation | |
| CN106179431A (en) | A kind of zinc titanium metal composite oxide and preparation thereof and application | |
| CN104292078B (en) | A kind of preparation method of bisphenol b | |
| CN104370748B (en) | High selectivity produces the method for triethylamine | |
| CN101857239B (en) | Preparation method of composite hollow silicate | |
| CN105289718B (en) | A kind of catalyst for synthesizing 3,3,3 trifluoroacetic acid ethyl esters and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160113 Termination date: 20170424 |