CN103274942A - Method for preparing ethyl levulinate based on solid superacid catalysis and furfuryl alcohol alcoholysis - Google Patents

Method for preparing ethyl levulinate based on solid superacid catalysis and furfuryl alcohol alcoholysis Download PDF

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CN103274942A
CN103274942A CN2013102673590A CN201310267359A CN103274942A CN 103274942 A CN103274942 A CN 103274942A CN 2013102673590 A CN2013102673590 A CN 2013102673590A CN 201310267359 A CN201310267359 A CN 201310267359A CN 103274942 A CN103274942 A CN 103274942A
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strong acid
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furfuryl alcohol
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曾宪海
赵耿
孙勇
林鹿
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Xiamen University
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Xiamen University
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Abstract

The invention discloses a method for preparing ethyl levulinate based on solid superacid catalysis and furfuryl alcohol alcoholysis, and relates to ethyl levulinate. The method comprises the steps of adding furfuryl alcohol, a catalyst and a reaction solvent to a reaction kettle, reacting, and obtaining ethyl levulinate. The catalyst is selected from at least one of solid superacid of SO4<2->/TiO2, SO4<2->/ZrO2, SO4<2->/Fe2O3, SO4<2->/SnO2, and SO4<2->/Al2O3, or at least one of solid superacid of S2O8<2->/TiO2, S2O8<2->/ZrO2, S2O8<2->/Fe2O3, S2O8<2->/SnO2, and S2O8<2->/Al2O3; the reaction solvent is ethyl alcohol; and reaction conditions are that the temperature is 100-150 DEG C, the rotating speed is 300-500 rpm (revolutions per minute), the time is 0.5-2.5h, a mass ratio of furfuryl alcohol to solid superacid is (1-4):1, and a mass ratio of furfuryl alcohol to ethyl alcohol is (0.01-0.2):1.

Description

Alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol
Technical field
The present invention relates to ethyl levulinate, relate to especially that a kind of alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol.
Background technology
Along with the continuous consumption of Nonrenewable resources such as coal, oil, human society faces unprecedented resource and energy dilemma.Biomass are a kind of renewable resourcess, have enormous amount, cheap, can realize advantages such as carbon cycle, utilize biomass resource to prepare the focus that fuel and chemical have become domestic and international research.Can prepare the kinds of platform compound from biomass resource, ethyl levulinate is exactly one of them.
Ethyl levulinate contains a carbonyl and an ester group, and the two keys of the carbon-oxygen on the carbonyl are strong polar link, and carbon atom is center of positive charge, and when carbonyl reacted, the electrophilic center of carbon atom played a part decision.Therefore, ethyl levulinate has good reaction activity, and reactions such as hydrolysis, transesterify, addition, replacement, redox can take place.Ethyl levulinate is a kind of important organic chemicals, can directly be used as spices, foodstuff additive, gasoline dope and biological liquid fuel etc., is widely used in many industries such as food, makeup, medicine, plastics and communications and transportation.
The method for preparing ethyl levulinate mainly contains three kinds: levulinic acid esterification method, the direct alcoholysis method of biomass and furfuryl alcohol alcoholysis method.At present, ethyl levulinate mainly is to carry out esterification by levulinic acid and ethanol under the catalysis of acid or enzyme to obtain.This synthetic method has reaction efficiency height, by product is few, reaction conditions is gentle advantage, but this method is raw material with the levulinic acid, causes production cost too high.The biomass alcoholysis method is with the disposable adding reactor of biomass material, catalyzer and ethanol, carries out alcoholysis under hot conditions, directly generates the method for ethyl levulinate.Chinese patent CN101709033A discloses the method for preparing methyl ester levulinate by alcoholysis of hexamylose in a kind of near-critical methanol, and this method is raw material with the biomass sugar, the advantage that technology is simple, cost is low is arranged, but reaction conditions is more violent, and energy consumption is bigger.The furfuryl alcohol alcoholysis method refers to utilize furfuryl alcohol and ethanol, by hydrolysis, open loop and rearrangement reaction, generates the method for ethyl levulinate under acidic conditions, and wherein feed ethanol and furfuryl alcohol can be obtained by Wood Adhesives from Biomass.Chinese patent CN102405205A has announced and has made furfuryl alcohol be converted into the method for ethyl levulinate in a kind of one-step reaction, this method is catalyzer with inorganic liquid acid, though reaction conditions gentleness, reaction times is short, by product is less, but be catalyzer with the liquid acid, can produce a large amount of liquid and waste slag producedly, and have problems such as product is difficult to separate, equipment corrosion is serious, not meet the direction of current Green Chemistry development.
In recent years, solid super strong acid substitution mineral acid catalysis ketal, aldolization and esterification have very high activity, and have not water funk, high temperature resistant, easy to make, three-waste pollution is few, catalyzer and advantages such as product is easy to separate.SO 4 2-/ M xO yType and S 2O 8 2-/ M xO yOneself causes people's attention the solid super-strong acid of type, uses novel solid super-strong acid to be catalyzer, to utilizing biomass resource synthesis of acetyl ethyl propionate significant.
Summary of the invention
The object of the present invention is to provide that a kind of alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol.
Concrete steps of the present invention are as follows:
Furfuryl alcohol, catalyzer and reaction solvent are added in the reactor, namely get ethyl levulinate after the reaction.
Described catalyzer can be selected from SO 4 2 –/ TiO 2Solid super-strong acid, SO 4 2 –/ ZrO 2Solid super-strong acid, SO 4 2-/ Fe 2O 3Solid super-strong acid, SO 4 2-/ SnO 2Solid super-strong acid, SO 4 2-/ Al 2O 3At least a in the solid super-strong acid etc., or S 2O 8 2 –/ TiO 2Solid super-strong acid, S 2O 8 2 –/ ZrO 2Solid super-strong acid, S 2O 8 2-/ Fe 2O 3Solid super-strong acid, S 2O 8 2-/ SnO 2Solid super-strong acid, S 2O 8 2-/ Al 2O 3At least a in the solid super-strong acid etc.; Reaction solvent is ethanol; The condition of described reaction can be: 100～150 ℃ of temperature of reaction, mixing speed 300～500rpm, reaction times 0.5～2.5h; The mass ratio of described furfuryl alcohol and solid super-strong acid can be (1～4): 1, and the mass ratio of described furfuryl alcohol and ethanol can be (0.01～0.2): 1.
Described SO 4 2 –/ TiO 2The preparation method of solid super-strong acid is as follows: be the TiCl of 100g/L with concentration 4Be dissolved in the distilled water, add ammoniacal liquor again to pH=9, ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L sulfuric acid in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described SO 4 2 –/ ZrO 2The preparation method of solid super-strong acid is as follows: be the ZrOCl of 100g/L with concentration 28H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L sulfuric acid in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described SO 4 2-/ Fe 2O 3The preparation method of solid super-strong acid is as follows: be the FeCl of 100g/L with concentration 36H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L sulfuric acid in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described SO 4 2-/ SnO 2The preparation method of solid super-strong acid is as follows: be the SnCl of 100g/L with concentration 45H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With 3.0mol/L sulfuric acid dipping 1h, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described SO 4 2-/ Al 2O 3The preparation method of solid super-strong acid is as follows: be the AlCl of 100g/L with concentration 36H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With 2.5mol/L sulfuric acid dipping 1h, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described S 2O 8 2 –/ TiO 2The preparation method of solid super-strong acid is as follows: be the TiCl of 100g/L with concentration 4Be dissolved in the distilled water, add ammoniacal liquor again to pH=9, ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L ammonium persulphate in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described S 2O 8 2 –/ ZrO 2The preparation method of solid super-strong acid is as follows: be the ZrOCl of 100g/L with concentration 28H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L ammonium persulphate in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described S 2O 8 2-/ Fe 2O 3The preparation method of solid super-strong acid is as follows: be the FeCl of 100g/L with concentration 36H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L ammonium persulphate in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described S 2O 8 2-/ SnO 2The preparation method of solid super-strong acid is as follows: be the SnCl of 100g/L with concentration 45H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With 3.0mol/L ammonium persulphate dipping 1h, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
Described S 2O 8 2-/ Al 2O 3The preparation method of solid super-strong acid is as follows: be the AlCl of 100g/L with concentration 36H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With 2.5mol/L ammonium persulphate dipping 1h, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
The invention has the advantages that with the solid super-strong acid to be catalyzer, this catalyzer can the alcoholysis of efficient catalytic furfuryl alcohol prepare ethyl levulinate, this Preparation of Catalyst is simple, with low cost, can reuse, compare with existing catalyzer not water funk, high temperature resistant, three-waste pollution is few, catalyzer is easily separated, can the alcoholysis of highly selective catalysis furfuryl alcohol prepare ethyl levulinate, by product is few.In addition, reaction system of the present invention is simple, and is environmentally friendly, and production cost is low, and convenient post-treatment has a good application prospect.
Description of drawings
Fig. 1 is the gas chromatogram of furfuryl alcohol and ethyl levulinate standard substance.X-coordinate is retention time (min) among the figure, and ordinate zou is chromatographic peak peak height (pA).
Fig. 2 is the gas chromatogram that the alcoholysis of solid superacid as catalyst furfuryl alcohol generates product.X-coordinate is retention time (min) among the figure, and ordinate zou is chromatographic peak peak height (pA).
Embodiment
The invention will be further described below in conjunction with embodiment, need to prove, embodiment does not constitute the restriction to the claimed scope of the present invention.
Embodiment 1:
With 1mL furfuryl alcohol, 0.5g solid super-strong acid SO 4 2 –/ TiO 2Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 125 ℃, keeps this thermotonus 2h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, get supernatant and carry out analyzing and testing, through gas chromatographic analysis, after gas-chromatography standard diagram (seeing Fig. 1 and Fig. 2) contrast of furfuryl alcohol and ethyl levulinate, calculate product ethyl levulinate productive rate and can reach 68.3%.
Embodiment 2:
With 1mL furfuryl alcohol, 0.5g solid super-strong acid SO 4 2 –/ ZrO 2Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 125 ℃, keeps this thermotonus 2h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, to get supernatant and carry out analyzing and testing, the ethyl levulinate productive rate is calculated in gas chromatographic analysis can reach 64.3%.
Embodiment 3:
With 1mL furfuryl alcohol, 0.5g solid super-strong acid S 2O 8 2-/ SnO 2Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 125 ℃, keeps this thermotonus 2h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, to get supernatant and carry out analyzing and testing, the ethyl levulinate productive rate is calculated in gas chromatographic analysis can reach 65.5%.
Embodiment 4:
With 1mL furfuryl alcohol, 0.5g solid super-strong acid S 2O 8 2-/ Al 2O 3Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 125 ℃, keeps this thermotonus 2h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, to get supernatant and carry out analyzing and testing, the ethyl levulinate productive rate is calculated in gas chromatographic analysis can reach 63.8%.
Embodiment 5:
With 1mL furfuryl alcohol, 0.5g solid super-strong acid SO 4 2 –/ TiO 2Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 100 ℃, keeps this thermotonus 2.5h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, to get supernatant and carry out analyzing and testing, the ethyl levulinate productive rate is calculated in gas chromatographic analysis can reach 35.5%.
Embodiment 6:
With 1mL furfuryl alcohol, 0.5g solid super-strong acid SO 4 2 –/ TiO 2Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 150 ℃, keeps this thermotonus 1.5h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, to get supernatant and carry out analyzing and testing, the ethyl levulinate productive rate is calculated in gas chromatographic analysis can reach 71.0%.
Embodiment 7:
With 1mL furfuryl alcohol, 0.25g solid super-strong acid SO 4 2 –/ TiO 2Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 100 ℃, keeps this thermotonus 1.5h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, to get supernatant and carry out analyzing and testing, the ethyl levulinate productive rate is calculated in gas chromatographic analysis can reach 50.3%.
Embodiment 8:
With 0.5mL furfuryl alcohol, 0.5g solid super-strong acid SO 4 2 –/ TiO 2Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 125 ℃, keeps this thermotonus 2.5h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, to get supernatant and carry out analyzing and testing, the ethyl levulinate productive rate is calculated in gas chromatographic analysis can reach 81.4%.
Embodiment 9:
With 2mL furfuryl alcohol, 0.5g solid super-strong acid SO 4 2 –/ TiO 2Join in the lump in the 50mL reactor with 20mL ethanol, begin reaction after airtight, mixing speed is 500rpm, treats to pick up counting when temperature is elevated to 125 ℃, keeps this thermotonus 2.5h, behind the question response bundle, reactor is immersed be cooled to room temperature in the cold water immediately.Reaction solution is centrifugal under 10000rpm, to get supernatant and carry out analyzing and testing, the ethyl levulinate productive rate is calculated in gas chromatographic analysis can reach 58.7%.

Claims (7)

1. alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol, it is characterized in that its concrete steps are as follows: furfuryl alcohol, catalyzer and reaction solvent are added in the reactor, namely get ethyl levulinate after the reaction.
2. alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol according to claim 1, it is characterized in that described catalyzer is selected from SO 4 2 –/ TiO 2Solid super-strong acid, SO 4 2 –/ ZrO 2Solid super-strong acid, SO 4 2-/ Fe 2O 3Solid super-strong acid, SO 4 2-/ SnO 2Solid super-strong acid, SO 4 2-/ Al 2O 3At least a in the solid super-strong acid, or
S 2O 8 2 –/ TiO 2Solid super-strong acid, S 2O 8 2 –/ ZrO 2Solid super-strong acid, S 2O 8 2-/ Fe 2O 3Solid super-strong acid, S 2O 8 2-/ SnO 2Solid super-strong acid, S 2O 8 2-/ Al 2O 3At least a in the solid super-strong acid.
3. alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol according to claim 1, it is characterized in that described reaction solvent is ethanol.
4. alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol according to claim 1, it is characterized in that the condition of described reaction is: 100～150 ℃ of temperature of reaction, mixing speed 300～500rpm, reaction times 0.5～2.5h.
5. alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol according to claim 1, the mass ratio that it is characterized in that described furfuryl alcohol and solid super-strong acid is (1～4): 1, and the mass ratio of described furfuryl alcohol and ethanol is (0.01～0.2): 1.
6. as alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol as described in the claim 2, it is characterized in that described SO 4 2 –/ TiO 2The preparation method of solid super-strong acid is as follows: be the TiCl of 100g/L with concentration 4Be dissolved in the distilled water, add ammoniacal liquor again to pH=9, ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L sulfuric acid in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid;
Described SO 4 2 –/ ZrO 2The preparation method of solid super-strong acid is as follows: be the ZrOCl of 100g/L with concentration 28H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L sulfuric acid in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid;
Described SO 4 2-/ Fe 2O 3The preparation method of solid super-strong acid is as follows: be the FeCl of 100g/L with concentration 36H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L sulfuric acid in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid;
Described SO 4 2-/ SnO 2The preparation method of solid super-strong acid is as follows: be the SnCl of 100g/L with concentration 45H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With 3.0mol/L sulfuric acid dipping 1h, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid;
Described SO 4 2-/ Al 2O 3The preparation method of solid super-strong acid is as follows: be the AlCl of 100g/L with concentration 36H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With 2.5mol/L sulfuric acid dipping 1h, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
7. as alcoholysis prepares the method for ethyl levulinate based on the solid superacid as catalyst furfuryl alcohol as described in the claim 2, it is characterized in that described S 2O 8 2 –/ TiO 2The preparation method of solid super-strong acid is as follows: be the TiCl of 100g/L with concentration 4Be dissolved in the distilled water, add ammoniacal liquor again to pH=9, ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L ammonium persulphate in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid;
Described S 2O 8 2 –/ ZrO 2The preparation method of solid super-strong acid is as follows: be the ZrOCl of 100g/L with concentration 28H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L ammonium persulphate in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid;
Described S 2O 8 2-/ Fe 2O 3The preparation method of solid super-strong acid is as follows: be the FeCl of 100g/L with concentration 36H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With the ratio dipping 1h of 0.5mol/L ammonium persulphate in 15mL/g, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid;
Described S 2O 8 2-/ SnO 2The preparation method of solid super-strong acid is as follows: be the SnCl of 100g/L with concentration 45H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With 3.0mol/L ammonium persulphate dipping 1h, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid;
Described S 2O 8 2-/ Al 2O 3The preparation method of solid super-strong acid is as follows: be the AlCl of 100g/L with concentration 36H 2O is dissolved in the distilled water, adds ammoniacal liquor again to pH=9, and ageing is filtered, and washing is to there not being Cl –, 110 ℃ of following dry back porphyrizes; With 2.5mol/L ammonium persulphate dipping 1h, filter, 110 ℃ are dry down, 500 ℃ of following roastings, namely get SO 4 2 –/ TiO 2Solid super-strong acid.
CN2013102673590A 2013-06-28 2013-06-28 Method for preparing ethyl levulinate based on solid superacid catalysis and furfuryl alcohol alcoholysis Pending CN103274942A (en)

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CN108722443A (en) * 2017-04-19 2018-11-02 中国科学院化学研究所 A kind of Al2O3Modified SO42-/SnO2The preparation method and application of solid acid catalyst
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CN105646227B (en) * 2014-11-14 2018-02-09 上海交通大学 A kind of method that levulinate is prepared using furfuryl alcohol
CN104801331A (en) * 2015-04-24 2015-07-29 南京工业大学 Method for preparing catalyst with excellent performance in epoxyethylbenzene alcoholysis by use of methanol at room temperature
CN104801331B (en) * 2015-04-24 2018-01-05 南京工业大学 A kind of preparation method of the catalyst with room temperature Methanolysis Styryl oxide performance
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CN111250113A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Application of super acidic catalyst in direct synthesis of adiponitrile from adipic acid
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CN110681401A (en) * 2019-05-28 2020-01-14 济南大学 Preparation method of expanded graphite carbon-based solid acid catalyst
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Application publication date: 20130904