CN103877965A - Preparation method and application of tin dioxide-based solid super basic catalyst - Google Patents
Preparation method and application of tin dioxide-based solid super basic catalyst Download PDFInfo
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Abstract
The invention discloses a tin dioxide-based solid super basic catalyst which comprises the following components: 70wt%-90wt% of tin dioxide and 10wt%-30wt% of a modification component, wherein the modification component is potassium hydroxide, potassium nitrate, potassium fluoride or potassium carbonate. The invention further provides a preparation method and catalytic application of the solid super basic catalyst. The solid super basic catalyst provided by the invention is simple in composition and high in catalytic activity and selectivity, and can be applied to various types of catalytic reactions.
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) exceed the solid alkaline material of 19 units.Solid super base shows excellent performance in multiple reaction as catalyst: (1) catalytic activity is high, reaction condition gentleness; (2) selectively 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 easily inactivation of coking.
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 that this class catalyst is difficult to the one of the main reasons in industrial large-scale application.Rare earth oxide is water insoluble, and has and similarly alkalescence of alkaline earth oxide, and the composite oxides of rare earth and other element composition likely become the super basic catalyst of function admirable especially.Therefore, employing 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 mechanism has 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, is also the important synthon that builds other heterocyclic compounds, and its benzo derivative has multiple physiologically active and pharmacologically active.4H-pyrans mainly synthesizes by aldehydes, malononitrile and active methylene one kettle way, and the catalyst using 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, catalyst is non-renewable; And after reaction, produce waste water, to shortcomings such as environment are unfriendly.In order to overcome these shortcomings, chemist is just making great efforts to develop highly active solid base recently.For example N.Seshu Babu has reported that magnesium lanthanium complex oxide catalysis aromatic aldehyde, malononitrile and ethyl acetoacetate synthesize 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, needed reaction temperature is high, and the reaction time is long, and productive rate is low.
Deficiency in reacting with the ternary condensation of active methylene compound for existing solid base catalyst and aldehyde, malononitrile, 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 take single metal oxide as major constituent, and it prepares simple and easy to do, and catalyst amount is little, has higher activity, selective and stability.
The concrete scheme of realizing the object of the invention is: a kind of preparation method of tin dioxide solid super basic catalyst is provided, and the step comprising is:
Get crystallization butter of tin wiring solution-forming, with KOH or the NH of 1mol/L
3h
2o regulator solution pH=6～8, centrifugation, wash 4～5 times, then by the sediment wiring solution-forming obtaining, add graphene oxide solution, reflux digestion 12～72h, centrifugation, dried overnight, is then placed in sediment Muffle furnace and is progressively warming up to 400～700 ℃, roasting 1～5h, makes tin ash; Get respectively the modification component of the above-mentioned tin ash making of 70wt%-90wt% and 10wt%-30wt%, grind and be placed in tube furnace in N
2or under atmosphere of inert gases, being warming up to 400～700 ℃, heat treatment 1～5h, makes solid super basic catalyst; Wherein, described modification component is at least one being selected from potassium hydroxide, potassium nitrate, potassium fluoride or potash.
In the preparation method of above-mentioned tin dioxide solid super basic catalyst, to prepare graphite oxide powder by modification Hummers method to the graphene oxide solution adding in described solution, 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 ℃, and heating rate is 1～10 ℃/min, and heat treatment time is 1～5h.
A further object of the present invention be to provide above-mentioned tin dioxide solid super basic catalyst catalysis aldehyde, malononitrile react with the ternary condensation of active methylene compound and Knoevenagel condensation reaction in application.
Above-mentioned tin dioxide solid super basic catalyst is being applied to that catalysis aldehyde, malononitrile react with the ternary condensation of active methylene compound and when Knoevenagel condensation reaction, 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 providing forms simple, catalytic activity and selectively high, prepare simple and easy to do, in the time that it is applied to catalytic reaction, catalyst amount is little, corrosion-free to reactor, belongs to environment-friendly catalyst, after reaction finishes, catalyst can be realized and being repeatedly used by centrifugation.
[Brief Description Of Drawings]
Figure 1 shows that the CO of embodiment 1 and comparative example 1,2 prepared catalyst
2-TPD comparison diagram; Wherein curve a is the 20%KOH/SnO that adds graphene oxide to prepare
2, curve b does not add 20%KOH/SnO prepared by graphene oxide
2, curve c is the SnO that adds graphene oxide to prepare
2.
[specific embodiment]
Embodiment 1
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit stir, limit is added drop-wise to the KOH of 1mol/L in solution by constant pressure funnel, to the pH of solution be 6-8, stop drip, continue stir 3h; Centrifugation, washes 4～5 times, and sediment is dissolved in to 60mL water wiring solution-forming again; Drip the graphene oxide solution that 60mL concentration is 2g/L, in oil bath, be warming up to 103 ℃, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rise to 550 ℃ by room temperature with 5 ℃/min, and keep 3h at 550 ℃, obtain SnO
2; Get 80wt%SnO
2and 20wt%KOH, being placed in mortar, the grinding that adds water, dries, and is finally placed in tube furnace in N
2under atmosphere, be warming up to 550 ℃ of after-baking 3h, make 20% potassium doped stannum oxide solid super basic catalyst.
Take respectively 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is made joins in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 98.1%, product be selectively greater than 99.0%.
The CO of the prepared catalyst of the present embodiment
2-TPD schemes 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 stir, limit is added drop-wise to the KOH of 1mol/L in solution by constant pressure funnel, to the pH of solution be 6-8, stop drip, continue stir 3h; Centrifugation, washes 4～5 times, and sediment is dissolved in to 60mL water wiring solution-forming again; Drip the graphene oxide solution that 60mL concentration is 2g/L, 180 ℃ of crystallization 24h, centrifugation, dried overnight, then in roaster, rise to 550 ℃ by room temperature with 5 ℃/min, and keep 3h at 550 ℃, obtain SnO
2; Get 80wt%SnO
2and 20wt%KOH, being placed in mortar, the grinding that adds water, dries, and is finally placed in tube furnace in N
2under atmosphere, be warming up to 550 ℃ of after-baking 3h, make 20% potassium doped stannum oxide solid super basic catalyst.
Take respectively 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is made joins in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 91.7%, product be selectively greater than 99.0%.
Embodiment 3
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit stir, limit is added drop-wise to the KOH of 1mol/L in solution by constant pressure funnel, to the pH of solution be 6-8, stop drip, continue stir 3h; Centrifugation, washes 4～5 times, and sediment is dissolved in to 60mL water wiring solution-forming again; Drip the graphene oxide solution that 60mL concentration is 2g/L, in oil bath, be warming up to 103 ℃, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rise to 550 ℃ by room temperature with 5 ℃/min, and keep 3h at 550 ℃, obtain SnO
2; Get 90wt%SnO
2and 10wt%KOH, being placed in mortar, the grinding that adds water, dries, and is finally placed in tube furnace in N
2under atmosphere, be warming up to 550 ℃ of after-baking 3h, make 10% potassium doped stannum oxide solid super basic catalyst.
Take respectively 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is made joins in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 85.5%, product be selectively greater than 99.0%.
Embodiment 4
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit stir, limit is added drop-wise to the KOH of 1mol/L in solution by constant pressure funnel, to the pH of solution be 6-8, stop drip, continue stir 3h; Centrifugation, washes 4～5 times, and sediment is dissolved in to 60mL water wiring solution-forming again; Drip the graphene oxide solution that 60mL concentration is 2g/L, in oil bath, be warming up to 103 ℃, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rise to 550 ℃ by room temperature with 5 ℃/min, and keep 3h at 550 ℃, obtain SnO
2; Get 70wt%SnO
2and 30wt%KOH, being placed in mortar, the grinding that adds water, dries, and is finally placed in tube furnace in N
2under atmosphere, be warming up to 550 ℃ of after-baking 3h, make 30% potassium doped stannum oxide solid super basic catalyst.
Take respectively 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is made joins in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 95.1%, product be selectively greater than 99.0%.
Embodiment 5
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit stir, limit is added drop-wise to the KOH of 1mol/L in solution by constant pressure funnel, to the pH of solution be 6-8, stop drip, continue stir 3h; Centrifugation, washes 4～5 times, and sediment is dissolved in to 60mL water wiring solution-forming again; Drip the graphene oxide solution that 60mL concentration is 2g/L, in oil bath, be warming up to 103 ℃, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rise to 550 ℃ by room temperature with 5 ℃/min, and keep 3h at 550 ℃, obtain SnO
2; Get 80wt%SnO
2and 20wt%KNO
3, being placed in mortar, the grinding that adds water, dries, and is finally placed in tube furnace in N
2under atmosphere, be warming up to 550 ℃ of after-baking 3h, make 20% potassium doped stannum oxide solid super basic catalyst.
Take respectively 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is made joins in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 82.5%, product be selectively greater than 99.0%.
Embodiment 6
Take 7.012 grams of SnCl
45H
2o is dissolved in 100mL water, wiring solution-forming; Limit stir, limit is added drop-wise to the KOH of 1mol/L in solution by constant pressure funnel, to the pH of solution be 6-8, stop drip, continue stir 3h; Centrifugation, washes 4～5 times, and sediment is dissolved in to 60mL water wiring solution-forming again; Drip the graphene oxide solution that 60mL concentration is 2g/L, in oil bath, be warming up to 103 ℃, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rise to 550 ℃ by room temperature with 5 ℃/min, and keep 3h at 550 ℃, obtain SnO
2; Get 80wt%SnO
2and 20wt%KF, being placed in mortar, the grinding that adds water, dries, and is finally placed in tube furnace in N
2under atmosphere, be warming up to 550 ℃ of after-baking 3h, make 20% potassium doped stannum oxide solid super basic catalyst.
Take respectively 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is made joins in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 96.3%, product be selectively greater than 99.0%.
Embodiment 7
Take respectively 0.212 gram of benzaldehyde and 0.132 gram of malononitrile, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 97.4%, product be selectively greater than 99.0%.
Embodiment 8
Take respectively 0.280 gram of 4-chloro-benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 94.5%, product be selectively greater than 99.0%.
Embodiment 9
Take respectively 0.280 gram of 4-chloro-benzaldehyde and 0.132 gram of malononitrile, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 96.1%, product be selectively greater than 99.0%.
Embodiment 10
Take respectively 0.240 gram of p-tolyl aldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 95.9%, product be selectively greater than 99.0%.
Embodiment 11
Take respectively 0.240 gram of p-tolyl aldehyde and 0.132 gram of malononitrile, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 98.2%, product be selectively greater than 99.0%.
Embodiment 12
Take respectively 0.302 gram of paranitrobenzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 92.2%, product be selectively greater than 99.0%.
Embodiment 13
Take respectively 0.302 gram of paranitrobenzaldehyde and 0.132 gram of malononitrile, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 90.2%, product be selectively greater than 99.0%.
Embodiment 14
Take respectively 0.212 gram of benzaldehyde, 0.286 gram of ethyl acetoacetate and 0.146 gram of malononitrile, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 2h, filters, catalyst is separated with reactant liquor, and reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 93.4%.
Embodiment 15
Take respectively 0.280 gram of 4-chloro-benzaldehyde, 0.286 gram of ethyl acetoacetate and 0.146 gram of malononitrile, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 2h, filters, catalyst is separated with reactant liquor, and reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 90.2%.
Embodiment 16
Take respectively 0.302 gram of paranitrobenzaldehyde, 0.286 gram of ethyl acetoacetate and 0.146 gram of malononitrile, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 2h, filters, catalyst is separated with reactant liquor, and reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 87.6%.
Embodiment 17
Take respectively 0.240 gram of p-tolyl aldehyde, 0.286 gram of ethyl acetoacetate and 0.146 gram of malononitrile, add in reaction vessel, add 2ml DMF as solvent, 0.050 gram of solid super basic catalyst being made by example 1 is joined in reactor; Under stirring condition, room temperature reaction 2h, filters, catalyst is separated with reactant liquor, and 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 stir, limit is added drop-wise to the KOH of 1mol/L in solution by constant pressure funnel, to the pH of solution be 6-8, stop drip, continue stir 3h; Centrifugation, washes 4～5 times, and sediment is dissolved in to 60mL water wiring solution-forming again; Drip the graphene oxide solution that 60mL concentration is 2g/L, in oil bath, be warming up to 103 ℃, condensing reflux 24h, centrifugation, dried overnight, then in roaster, rise to 550 ℃ by room temperature with 5 ℃/min, and keep 3h at 550 ℃, obtain tin oxide solid base catalyst.
Take respectively 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2ml DMF as solvent, the solid super basic catalyst that 0.050 gram of this example is made joins in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 55.4%, product be selectively greater than 99.0%.
The catalyst (c) that this comparative example makes and the CO of the prepared catalyst of embodiment 1 (a)
2as shown in Figure 1, result shows-TPD comparison diagram: the prepared catalyst (a) of embodiment 1 has a very large desorption peaks in the time of 70min, illustrates that the introducing of K has had obvious lifting to its base strength.
Comparative example 2
Embodiment 1 prepare tin ash process in do not add graphite oxide solution, then by the tin ash of preparing with modify component and carry out subsequent reactions and make solid super basic catalyst.
Take respectively 0.212 gram of benzaldehyde and 0.226 gram of ethyl cyanoacetate, add in reaction vessel, add 2mlDMF as solvent, the solid super basic catalyst that 0.050 gram of this example is made joins in reactor; Under stirring condition, room temperature reaction 15min, filter, catalyst is separated with reactant liquor, reactant liquor gas chromatographic analysis, the conversion ratio of benzaldehyde is 86.0%, product be selectively greater than 99.0%
The catalyst (b) that this comparative example makes and the CO of the prepared catalyst of embodiment 1 (a)
2as shown in Figure 1, result shows-TPD comparison diagram: the prepared catalyst of embodiment 1 (a) occurs larger desorption peaks in 70min left and right, has illustrated and has added the catalyst that graphene oxide is prepared to have higher base strength and alkali number.
Claims (5)
1. the method that prepared by tin dioxide solid super basic catalyst, is characterized in that, comprises following steps: get crystallization butter of tin wiring solution-forming, with KOH or the NH of 1mol/L
3h
2o regulator solution pH=6～8, centrifugation, wash 4～5 times, then by the sediment wiring solution-forming obtaining, add graphene oxide solution, reflux digestion 12～72h, centrifugation, dried overnight, is then placed in sediment Muffle furnace and is progressively warming up to 400～700 ℃, roasting 1～5h, makes tin ash; Get respectively the modification component of tin ash and the 10wt%-30wt% of the above-mentioned preparation of 70wt%-90wt%, grind and be placed in tube furnace in N
2or under atmosphere of inert gases, being warming up to 400～700 ℃, heat treatment 1～5h, makes solid super basic catalyst;
Wherein, described modification component is at least one being selected from potassium hydroxide, potassium nitrate, potassium fluoride or potash.
2. the preparation method of tin dioxide solid super basic catalyst according to claim 1, it is characterized in that, the graphite oxide powder standby by modification Hummers legal system to the graphene oxide solution adding in described solution, add water and make the solution of 2g/L, then the graphene oxide solution obtaining through ultrasonic processing 2h.
3. the preparation method of tin dioxide solid super basic catalyst according to claim 1, is characterized in that, described heat-treat condition is N
2or atmosphere of inert gases, heat treatment temperature is 400～700 ℃, and heating rate is 1～10 ℃/min, and heat treatment time is 1～5h.
Tin dioxide solid super basic catalyst claimed in claim 1 catalysis aldehyde, malononitrile react with the ternary condensation of active methylene compound and Knoevenagel condensation reaction in application.
Tin dioxide solid super basic catalyst according to claim 4 catalysis aldehyde, malononitrile react with the ternary condensation of active methylene compound and Knoevenagel condensation reaction in application, it is characterized in that, the consumption of described catalyst accounts for the 5wt%～15wt% of reaction-ure mixture.
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| CN108558618A (en) * | 2018-05-28 | 2018-09-21 | 朱晓萍 | A method of preparing 2,3- difluorophenols |
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|---|---|---|---|---|
| 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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2014
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Patent 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 |
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| CN108558618A (en) * | 2018-05-28 | 2018-09-21 | 朱晓萍 | A method of preparing 2,3- difluorophenols |
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