CN103877965B - A kind of preparation and application of tin dioxide solid super basic catalyst - Google Patents
A kind of preparation and application of tin dioxide solid super basic catalyst Download PDFInfo
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Abstract
The invention discloses a kind of tin dioxide solid super basic catalyst, the tin ash and the 10wt%-30wt% that comprise 70wt%-90wt% modify component, and wherein modifying component is potassium hydroxide, potassium nitrate, potassium fluoride or potash.Present invention also offers preparation method and the catalytic applications thereof of this solid superbase catalyst.Solid super basic catalyst provided by the present invention composition is simple, catalytic activity and selective height, can be applicable in polytype catalytic reaction.
Description
[technical field]
The present invention relates to catalysis and organic chemical synthesis technical field, relate in particular to a kind of preparation and application of tin dioxide solid super basic catalyst.
[background technology]
Solid super base refers to that base strength (breathes out several H that do not write
-) be greater than 26, also can think strength ratio neutral substance (H
-=7) solid basic material of 19 units is exceeded.Solid super base shows excellent performance as catalyst in multiple reaction: (1) catalytic activity is high, and reaction condition is gentle; (2) selective high, product purity is high, easy and product separation, and technique is simple; (3) catalyst is reusable, also can use continuously; (4) little to consersion unit corrosivity, post processing is simple.In addition, solid super basic catalyst in various organic reactions unlike solid strong acid catalyst because of coking easy in inactivation.
Conventional alkali solid catalyst mainly contains alkaline earth oxide and hydroxide, alkali metal oxide, loading type alkali metal and alkali metal oxide etc.Although they have high activity, its active component is met water and is easily run off and inactivation, and this is the one of the main reasons that this kind of catalyst is difficult to industrially large-scale application.Rare earth oxide is water insoluble, and has the alkalescence similar with alkaline earth oxide, and the composite oxides that rare earth and other element form likely become the super basic catalyst of function admirable especially.Therefore, adopt composite oxides solid base catalyst can not only greatly enrich the kind of solid base, and the achievement in research of alkali division center and formation mechenism have scientific value and realistic meaning for designing and developing novel solid body base catalyst.
4H-pyrans is one of main fundamental structure unit of natural products, and be also the important synthon building other heterocyclic compounds, its benzo derivative has multiple physiologically active and pharmacologically active.4H-pyrans is mainly through aldehydes, malononitrile and active methylene one pot process, and the catalyst used is mainly the homogeneous catalysts such as alkali metal hydroxide, alkali metal alcoholates, quaternary ammonium salt, alkali ionic liquid, organic base.But these catalyst are difficult to and product separation, and catalyst is non-renewable; And produce waste water after reaction, to shortcomings such as environment are unfriendly.In order to overcome these shortcomings, recent chemist is just making great efforts to develop highly active solid base.Such as N.Seshu Babu reports magnesium lanthanium complex oxide catalysis aromatic aldehyde, malononitrile and ethyl acetoacetate synthesis 2-Amino 3 cyano-4-substituted-phenyl-5-methoxycarbonyl group-4H-pyrylium compound (Babu N S et al.Tetrahedron Letters49 (2008) 2730-2733).Although these catalyst have certain catalytic activity to this reaction, required reaction temperature is high, and the reaction time is long, and productive rate is low.
Deficiency in reacting for the ternary condensation of existing solid base catalyst and aldehyde, malononitrile and active methylene compound, industry attempts to develop some solid superbase catalyst always, and is applied to this catalytic reaction.
[summary of the invention]
The object of this invention is to provide a kind of preparation and application of tin dioxide solid super basic catalyst.This catalyst is with single metal oxide for major constituent, and it prepares simple and easy to do, and catalyst amount is little, has higher activity, selective and stability.
The concrete scheme realizing the object of the invention is: the preparation method providing a kind of tin dioxide solid super basic catalyst, and the step comprised is:
Get stannic chloride pentahydrate wiring solution-forming, with KOH or NH of 1mol/L
3h
2o regulates pH value of solution=6 ~ 8, centrifugation, wash 4 ~ 5 times, then the sediment wiring solution-forming that will obtain, add graphene oxide solution, reflux digestion 12 ~ 72h, centrifugation, dried overnight, is then placed in Muffle furnace and is progressively warming up to 400 ~ 700 DEG C by sediment, roasting 1 ~ 5h, obtained tin ash; Get the modification component of the above-mentioned obtained tin ash of 70wt%-90wt% and 10wt%-30wt% respectively, grinding is placed in tube furnace in N
2or be warming up to 400 ~ 700 DEG C under atmosphere of inert gases, heat treatment 1 ~ 5h, i.e. obtained solid super basic catalyst; Wherein, described modification component is selected from least one in potassium hydroxide, potassium nitrate, potassium fluoride or potash.
In the preparation method of above-mentioned tin dioxide solid super basic catalyst, the graphene oxide solution added in described solution prepares graphite oxide powder by modification Hummers method, add water and be mixed with the solution of 2g/L, ultrasonic 2h, obtains graphene oxide solution.
In the preparation method of above-mentioned tin dioxide solid super basic catalyst, described heat-treat condition is N
2or atmosphere of inert gases, heat treatment temperature is 400 ~ 700 DEG C, and heating rate is 1 ~ 10 DEG C/min, and heat treatment time is 1 ~ 5h.
Another object of the present invention is to provide above-mentioned tin dioxide solid super basic catalyst to react and application in Knoevenagel condensation reaction at the ternary condensation of catalysis aldehyde, malononitrile and active methylene compound.
Above-mentioned tin dioxide solid super basic catalyst the ternary condensation being applied to catalysis aldehyde, malononitrile and active methylene compound react and Knoevenagel condensation reaction time, the consumption of this catalyst accounts for the 5wt% ~ 15wt% of reaction-ure mixture.
Beneficial effect of the present invention is, the tin dioxide solid super basic catalyst composition provided is simple, catalytic activity and selective height, prepare simple and easy to do, when it is applied to catalytic reaction, catalyst amount is little, corrosion-free to reactor, belongs to environment-friendly catalyst, after reaction terminates, catalyst can realize repeatedly using by centrifugation.
[Brief Description Of Drawings]
Figure 1 shows that the CO of embodiment 1 and the catalyst obtained by comparative example 1,2
2-TPD comparison diagram; Wherein curve a adds 20%KOH/SnO prepared by graphene oxide
2, curve b does not add 20%KOH/SnO prepared by graphene oxide
2, curve c adds SnO prepared by graphene oxide
2.
[detailed description of the invention]
Embodiment 1
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit is stirred, while be added drop-wise in solution by constant pressure funnel by the KOH of 1mol/L, the pH to solution is 6-8, stops dripping, and continues to stir 3h; Centrifugation, washes 4 ~ 5 times, sediment is dissolved in again 60mL water wiring solution-forming; Dripping 60mL concentration is the graphene oxide solution of 2g/L, is warming up to 103 DEG C, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rises to 550 DEG C by room temperature with 5 DEG C/min in oil bath, and keeps 3h at 550 DEG C, obtains SnO
2; Get 80wt%SnO
2and 20wt%KOH, be placed in mortar, add water grinding, dries, be finally placed in tube furnace in N
2550 DEG C of after-baking 3h are warming up to, i.e. obtained 20% potassium doped stannum oxide solid super basic catalyst under atmosphere.
Take 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is obtained joins in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 98.1%, and the selective of product is greater than 99.0%.
The CO of the catalyst obtained by the present embodiment
2-TPD figure is as shown in (a) in accompanying drawing 1.
Embodiment 2
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit is stirred, while be added drop-wise in solution by constant pressure funnel by the KOH of 1mol/L, the pH to solution is 6-8, stops dripping, and continues to stir 3h; Centrifugation, washes 4 ~ 5 times, sediment is dissolved in again 60mL water wiring solution-forming; Dripping 60mL concentration is the graphene oxide solution of 2g/L, 180 DEG C of crystallization 24h, centrifugation, dried overnight, then in roaster, rises to 550 DEG C by room temperature with 5 DEG C/min, and keeps 3h at 550 DEG C, obtains SnO
2; Get 80wt%SnO
2and 20wt%KOH, be placed in mortar, add water grinding, dries, be finally placed in tube furnace in N
2550 DEG C of after-baking 3h are warming up to, i.e. obtained 20% potassium doped stannum oxide solid super basic catalyst under atmosphere.
Take 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is obtained joins in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 91.7%, and the selective of product is greater than 99.0%.
Embodiment 3
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit is stirred, while be added drop-wise in solution by constant pressure funnel by the KOH of 1mol/L, the pH to solution is 6-8, stops dripping, and continues to stir 3h; Centrifugation, washes 4 ~ 5 times, sediment is dissolved in again 60mL water wiring solution-forming; Dripping 60mL concentration is the graphene oxide solution of 2g/L, is warming up to 103 DEG C, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rises to 550 DEG C by room temperature with 5 DEG C/min in oil bath, and keeps 3h at 550 DEG C, obtains SnO
2; Get 90wt%SnO
2and 10wt%KOH, be placed in mortar, add water grinding, dries, be finally placed in tube furnace in N
2550 DEG C of after-baking 3h are warming up to, i.e. obtained 10% potassium doped stannum oxide solid super basic catalyst under atmosphere.
Take 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is obtained joins in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 85.5%, and the selective of product is greater than 99.0%.
Embodiment 4
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit is stirred, while be added drop-wise in solution by constant pressure funnel by the KOH of 1mol/L, the pH to solution is 6-8, stops dripping, and continues to stir 3h; Centrifugation, washes 4 ~ 5 times, sediment is dissolved in again 60mL water wiring solution-forming; Dripping 60mL concentration is the graphene oxide solution of 2g/L, is warming up to 103 DEG C, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rises to 550 DEG C by room temperature with 5 DEG C/min in oil bath, and keeps 3h at 550 DEG C, obtains SnO
2; Get 70wt%SnO
2and 30wt%KOH, be placed in mortar, add water grinding, dries, be finally placed in tube furnace in N
2550 DEG C of after-baking 3h are warming up to, i.e. obtained 30% potassium doped stannum oxide solid super basic catalyst under atmosphere.
Take 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is obtained joins in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 95.1%, and the selective of product is greater than 99.0%.
Embodiment 5
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit is stirred, while be added drop-wise in solution by constant pressure funnel by the KOH of 1mol/L, the pH to solution is 6-8, stops dripping, and continues to stir 3h; Centrifugation, washes 4 ~ 5 times, sediment is dissolved in again 60mL water wiring solution-forming; Dripping 60mL concentration is the graphene oxide solution of 2g/L, is warming up to 103 DEG C, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rises to 550 DEG C by room temperature with 5 DEG C/min in oil bath, and keeps 3h at 550 DEG C, obtains SnO
2; Get 80wt%SnO
2and 20wt%KNO
3, be placed in mortar, add water grinding, dries, be finally placed in tube furnace in N
2550 DEG C of after-baking 3h are warming up to, i.e. obtained 20% potassium doped stannum oxide solid super basic catalyst under atmosphere.
Take 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is obtained joins in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 82.5%, and the selective of product is greater than 99.0%.
Embodiment 6
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit is stirred, while be added drop-wise in solution by constant pressure funnel by the KOH of 1mol/L, the pH to solution is 6-8, stops dripping, and continues to stir 3h; Centrifugation, washes 4 ~ 5 times, sediment is dissolved in again 60mL water wiring solution-forming; Dripping 60mL concentration is the graphene oxide solution of 2g/L, is warming up to 103 DEG C, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rises to 550 DEG C by room temperature with 5 DEG C/min in oil bath, and keeps 3h at 550 DEG C, obtains SnO
2; Get 80wt%SnO
2and 20wt%KF, be placed in mortar, add water grinding, dries, be finally placed in tube furnace in N
2550 DEG C of after-baking 3h are warming up to, i.e. obtained 20% potassium doped stannum oxide solid super basic catalyst under atmosphere.
Take 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is obtained joins in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 96.3%, and the selective of product is greater than 99.0%.
Embodiment 7
Take 0.212 gram of benzaldehyde and 0.132 gram of malononitrile respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 97.4%, and the selective of product is greater than 99.0%.
Embodiment 8
Take 0.280 gram of 4-chloro-benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 94.5%, and the selective of product is greater than 99.0%.
Embodiment 9
Take 0.280 gram of 4-chloro-benzaldehyde and 0.132 gram of malononitrile respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 96.1%, and the selective of product is greater than 99.0%.
Embodiment 10
Take 0.240 gram of p-tolyl aldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 95.9%, and the selective of product is greater than 99.0%.
Embodiment 11
Take 0.240 gram of p-tolyl aldehyde and 0.132 gram of malononitrile respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 98.2%, and the selective of product is greater than 99.0%.
Embodiment 12
Take 0.302 gram of paranitrobenzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 92.2%, and the selective of product is greater than 99.0%.
Embodiment 13
Take 0.302 gram of paranitrobenzaldehyde and 0.132 gram of malononitrile respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 90.2%, and the selective of product is greater than 99.0%.
Embodiment 14
Take 0.212 gram of benzaldehyde, 0.286 gram of ethyl acetoacetate and 0.146 gram of malononitrile respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 2h, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 93.4%.
Embodiment 15
Take 0.280 gram of 4-chloro-benzaldehyde, 0.286 gram of ethyl acetoacetate and 0.146 gram of malononitrile respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 2h, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 90.2%.
Embodiment 16
Take 0.302 gram of paranitrobenzaldehyde, 0.286 gram of ethyl acetoacetate and 0.146 gram of malononitrile respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 2h, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 87.6%.
Embodiment 17
Take 0.240 gram of p-tolyl aldehyde, 0.286 gram of ethyl acetoacetate and 0.146 gram of malononitrile respectively, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram is obtained by example 1 is joined in reactor; Under agitation, room temperature reaction 2h, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 89.3%.
Comparative example 1
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit is stirred, while be added drop-wise in solution by constant pressure funnel by the KOH of 1mol/L, the pH to solution is 6-8, stops dripping, and continues to stir 3h; Centrifugation, washes 4 ~ 5 times, sediment is dissolved in again 60mL water wiring solution-forming; Dripping 60mL concentration is the graphene oxide solution of 2g/L, is warming up to 103 DEG C, condensing reflux 24h in oil bath, centrifugation, dried overnight, then in roaster, rise to 550 DEG C by room temperature with 5 DEG C/min, and keep 3h at 550 DEG C, obtain tin oxide solid base catalyst.
Take 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is obtained joins in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 55.4%, and the selective of product is greater than 99.0%.
The CO of the catalyst (c) that this comparative example is obtained and the catalyst (a) obtained by embodiment 1
2as shown in Figure 1, result shows-TPD comparison diagram: obtained by embodiment 1 catalyst (a) have a very large desorption peaks when 70min, illustrate that the introducing of K has had obvious lifting to its base strength.
Comparative example 2
Do not add graphite oxide solution in preparing in tin ash process of embodiment 1, then the tin ash prepared is carried out subsequent reactions with modification component and obtain solid super basic catalyst.
Take 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate respectively, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is obtained joins in reactor; Under agitation, room temperature reaction 15min, filter, be separated with reactant liquor by catalyst, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 86.0%, and the selective of product is greater than 99.0%
The CO of the catalyst (b) that this comparative example is obtained and the catalyst (a) obtained by embodiment 1
2as shown in Figure 1, result shows-TPD comparison diagram: the catalyst (a) obtained by embodiment 1 occurs larger desorption peaks at about 70min, describes to add the catalyst that graphene oxide prepares and have higher base strength and alkali number.
Claims (5)
1. the method prepared of tin dioxide solid super basic catalyst, is characterized in that, comprise following steps: get stannic chloride pentahydrate wiring solution-forming, with KOH or NH of 1mol/L
3h
2o regulates pH value of solution=6 ~ 8, centrifugation, wash 4 ~ 5 times, then the sediment wiring solution-forming that will obtain, add graphene oxide solution, reflux digestion 12 ~ 72h, centrifugation, dried overnight, is then placed in Muffle furnace and is progressively warming up to 400 ~ 700 DEG C by sediment, roasting 1 ~ 5h, obtained tin ash; Get the tin ash of the above-mentioned preparation of 70wt%-90wt% and the modification component of 10wt%-30wt% respectively, grinding is placed in tube furnace in N
2or be warming up to 400 ~ 700 DEG C under atmosphere of inert gases, heat treatment 1 ~ 5h, i.e. obtained solid super basic catalyst;
Wherein, described modification component is selected from least one in potassium hydroxide, potassium nitrate, potassium fluoride or potash.
2. the method prepared of tin dioxide solid super basic catalyst according to claim 1, it is characterized in that, the graphene oxide solution added in described solution is by the standby graphite oxide powder of modification Hummers legal system, add water and make the solution of 2g/L, then through the ultrasonic graphene oxide solution processing 2h and obtain.
3. the method prepared of tin dioxide solid super basic catalyst according to claim 1, it is characterized in that, described heat-treat condition is N
2or atmosphere of inert gases, heat treatment temperature is 400 ~ 700 DEG C, and heating rate is 1 ~ 10 DEG C/min, and heat treatment time is 1 ~ 5h.
4. tin dioxide solid super basic catalyst according to claim 1 reacts and application in Knoevenagel condensation reaction at the ternary condensation of catalysis aldehyde, malononitrile and active methylene compound.
5. tin dioxide solid super basic catalyst according to claim 4 reacts and application in Knoevenagel condensation reaction at the ternary condensation of catalysis aldehyde, malononitrile and active methylene compound, it is characterized in that, the consumption of described catalyst accounts for the 5wt% ~ 15wt% of reaction-ure mixture.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1632290A1 (en) * | 2003-04-23 | 2006-03-08 | Japan Energy Corporation | Solid acid catalyst containing tin and method for preparation thereof |
| CN101879457A (en) * | 2010-06-07 | 2010-11-10 | 湖南大学 | Novel nano-solid strong base catalyst, preparation method thereof and application thereof |
| CN101927178A (en) * | 2010-07-12 | 2010-12-29 | 湖南大学 | Solid super basic catalyst and preparation method and application thereof |
| CN102247827A (en) * | 2011-05-04 | 2011-11-23 | 湖南大学 | Novel nano solid super-strong alkali catalyst and preparation and application thereof |
| CN103212398A (en) * | 2013-02-25 | 2013-07-24 | 湖南大学 | Preparation and application of solid super alkali catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1632290A1 (en) * | 2003-04-23 | 2006-03-08 | Japan Energy Corporation | Solid acid catalyst containing tin and method for preparation thereof |
| CN101879457A (en) * | 2010-06-07 | 2010-11-10 | 湖南大学 | Novel nano-solid strong base catalyst, preparation method thereof and application thereof |
| CN101927178A (en) * | 2010-07-12 | 2010-12-29 | 湖南大学 | Solid super basic catalyst and preparation method and application thereof |
| CN102247827A (en) * | 2011-05-04 | 2011-11-23 | 湖南大学 | Novel nano solid super-strong alkali catalyst and preparation and application thereof |
| CN103212398A (en) * | 2013-02-25 | 2013-07-24 | 湖南大学 | Preparation and application of solid super alkali catalyst |
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