CN102795976A - Method for preparing diethoxymethane by using active carbon supported solid acid catalyst - Google Patents
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- CN102795976A CN102795976A CN2011101340399A CN201110134039A CN102795976A CN 102795976 A CN102795976 A CN 102795976A CN 2011101340399 A CN2011101340399 A CN 2011101340399A CN 201110134039 A CN201110134039 A CN 201110134039A CN 102795976 A CN102795976 A CN 102795976A
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- diethyl ether
- formaldehyde
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a method for preparing diethoxymethane by using an active carbon supported solid acid catalyst. The method is characterized in that formaldehyde and ethanol are used as raw materials and reacted under normal pressure under the action of a solid acid catalyst at the temperature of 70 to 100 DEG C, the reflux ratio is controlled to be 1:1-4:1, distillate of 74 to 76 DEG C is collected on the top of a tower, and the diethoxymethane product is obtained; after the aqueous solution in a tower kettle is filtered, the solid acid catalyst is recycled in the kettle; the molar ratio of the formaldehyde to the ethanol is 1:2-1:5, the formaldehyde raw material is a formaldehyde solution at the concentration of over 37 weight percent, and the ethanol raw material is absolute ethanol or an ethanol solution at the concentration of 75-95 weight percent; the solid acid catalyst is the active carbon supported solid acid catalyst, the active acid ingredient is sulfuric acid, and the acid solid capacity is 15 to 25 mass percent; and the consumption of the solid acid catalyst is 0.3 to 10 percent of the total mass of the reactants. The method has the advantages that the catalyst is economic in preparation, easy to separate from the product and low in equipment corrosion, and the waste catalyst is easy and convenient to reclaim and treat.
Description
Technical field
The present invention relates to the immobilized acid catalyst of a kind of gac and prepare the methylene diethyl ether method; Methylene diethyl ether is also claimed ethylal, and structural formula is: CH
3CH
2OCH
2O CH
2CH
3Belong to field of chemical technology.
Background technology
Methylene diethyl ether is a colourless transparent liquid, and molecular formula is C
5H
12O
2, molecular weight is 104.15,88 ℃ of pure article boiling points, and fusing point-66.50 ℃, solubleness is 9% (wt) in 20 ℃ of water, the good properties that has can be used for organic synthesis and extraction, dilution, recrystallization equal solvent.
Methylene diethyl ether is as the solvent in the organic synthesis; It is a kind of protophobic solvent; Avidity to water is very low, has water insoluble and nonhygroscopic character, does not therefore need further dry some reaction such as organic metal reactions to water sensitive that just can directly be used for; Methylene diethyl ether viscosity is low, is used for the big reaction of low-temp reaction and other viscosity and can makes post-reaction treatment simple, as in the reduction reaction of tetra lithium aluminium hydride, makes solvent with methylene diethyl ether, and aftertreatment is simple, and product purity is high; Methylene diethyl ether is stable to alkali, can be used for the differential responses under the highly basic condition.Some other all available methylene diethyl ether of reaction of being familiar with is made solvent, like alkylation, acylations, organolithium reaction and Grignard reaction and oxidizing reaction.
Methylene diethyl ether auxiliary agent, reaction reagent such as act as a fuel.As Equivalent, carbonylation reaction substrate, preparation phenylglycine derivatives and other amino acid of ethoxymethyl reagent, formaldehyde, as alcoholic acid source preparation ether and ester etc.
The methylene diethyl ether main preparation methods has: methylene dichloride method, dimethyl sulfoxide method, Calcium Chloride Method, formaldehyde and alcoholic acid acetal method, paraxin by-product method etc.
The methylene dichloride method is a synthetic methylene diethyl ether method early, and reaction not only needs sodium ethylate to make reagent, also requires waterless operation, adds that yield is low, is the method that is eliminated.
Methyl-sulphoxide is unstable to acid, and thermal degradation generates formaldehyde, and formaldehyde and ethanol carry out addition reaction and obtains methylene diethyl ether, this reaction by-product SO
2, environment is had pollution, thereby is unfavorable for scale operation.
The acetal method is to be reacted under the acid catalyst effect by formaldehyde and ethanol, and is simple to operate, and the reaction times is short, and yield is high, is comparatively ideal preparation method, also is the method that present investigator pays close attention to most.
In the production process of paraxin, generate by the urotropine solution of right-nitro-2-bromoacetophenone, in this solution, add the ethanolic soln of hydrochloric acid, the sub product methylene diethyl ether, many production of chloramphenicol producer utilizes this method to obtain methylene diethyl ether.
The present aldol condensation method of comparative maturity, synthesis technique adopt intermittently substantially, continuously and three kinds of operating method of catalytic distillation carry out.Classical aldol reaction uses mineral acid (like H
2SO
4, HF, H
3PO
4, tosic acid etc.) and Lewis acid (like A1C1
3, FeC1
3Deng) catalyzer, all have catalytic activity preferably, but have difficult separation and recycling, to shortcoming such as equipment corrosion is serious.People develop solid acid catalyst for this reason, like Zeo-karb, crystal aluminosilicate, HZSM-5, H
4SiW
12O
40/ SiO
2Heteropolyacid catalyst waits and replaces liquid acid, thereby establishes a kind of methylal reactive distillation novel process that supplies suitability for industrialized production.On the method for use of catalyzer; Can be with the loose filling of granules of catalyst; Also can catalyzer be scattered in container or the reaction tower with the mud form, also have catalyzer is wished the ring filling with drawing, the somebody places catalyzer in the cloth bag or with the back filling of Stainless Steel Cloth parcel and uses.
Summary of the invention
The object of the invention provide a kind of economical in reaction, catalyzer separate with product easily, little to equipment corrosion, the cleaning the methylene diethyl ether preparation method.
Technology contents of the present invention is: the immobilized acid catalyst of a kind of gac prepares the methylene diethyl ether method; It is characterized in that in the reaction kettle that has whisking appliance, rectifying tower formaldehyde and ethanol are raw material, under the solid acid catalyst effect, carry out paradoxical reaction and press; Temperature of reaction is 70～100 ℃; The control reflux ratio is 1 ﹕, 1～4 ﹕ 1, at 74～76 ℃ of fractions of overhead collection, makes the methylene diethyl ether product; After filtering out the tower still aqueous solution, catalyzer is stayed in the still and is recycled; Wherein formaldehyde and alcoholic acid mole proportioning are 1 ﹕, 2～1 ﹕ 5, and solid acid catalyst is the immobilized acid catalyst of gac, and the active ingredient acid of the immobilized acid catalyst of gac is sulfuric acid, and sour supported quantity is 15～25 quality %; The solid acid catalyst consumption is 0.3～10% of a reactant total mass.
It is thick product that the present invention makes methylene diethyl ether, and methylene diethyl ether content is about 60～70%, and all the other are mainly the second alcohol and water; Wherein methylene diethyl ether and water can form azeotrope, and the boiling point of azeotrope is 75.2 ℃, quality content 10%, and methylene diethyl ether and ethanol can form azeotrope, and the boiling point of azeotrope is 74.2 ℃, ethanol mass content 32%.This thick product removes second alcohol and water wherein through refining, can make purity greater than 99% product.
The present invention develops the immobilized acid catalyst system of a kind of gac, and such catalyst preparation process is simple, with sulfuric acid through with the effect of charcoal base after become insoluble solid acid.Though such catalyzer also is through the protonic acid position (SO on it
3H) play katalysis, but because-SO
3H and C key have formed covalent linkage, belong to hydrophobic material, and it can effectively absorb organic molecule and not absorb water.When water existed, it had avoided the protonic acid position to be prone to hydration takes place and the problem that reduces catalytic activity, and helped reactant to promote to react with contacting of acid position to carry out.
In the preparation method of above-mentioned methylene diethyl ether, the immobilized acid catalyst of gac is to be carrier with the gac, is immobilized thing with sulfuric acid; Its preparation process: gac is cleaned oven dry, 115～125 ℃ of activation 2～4 h with zero(ppm) water; Taking by weighing a certain amount of pretreated gac, to be immersed in 25～30 times of mass concentrations be in 60～98 quality % sulphuric acid solns; Stirring refluxes in 100～140 ℃ down floods 3～5 h, suction filtration, and washing is to neutral; 115～125 ℃ are dried to constant weight in baking oven, get the immobilized acid catalyst of gac after the cooling.This catalyst tolerates warm nature is good, and is little to equipment corrosion, and reaction can recycle after filtration can separate with product, realizes cleaner production.
In the preparation method of above-mentioned methylene diethyl ether, the suitable temperature of reaction of synthesis under normal pressure is 70～100 ℃, and reflux ratio is corresponding increase with the increase of temperature of reaction, and suitable tower top temperature is 74～76 ℃; Reaction finishes after-filtration, and the tower still aqueous solution is discharged, and solid acid catalyst is stayed in the reaction kettle and recycled; The suitable mole of formaldehyde and alcoholic acid proportioning is 1 ﹕, 2.2～1 ﹕ 4; The suitable mole of formaldehyde and alcoholic acid proportioning is 1 ﹕, 2.5～1 ﹕ 3; The amount of ethanol increase can improve the transformation efficiency of formaldehyde, thereby improves the methylene diethyl ether yield, but amount of ethanol too much can be brought ethanol and methylene diethyl ether product separation problem; Feed ethanol can be absolute ethyl alcohol, concentration is that the ethanolic soln of 75～95 quality % or the concentration of methylene diethyl ether purification back recovery are 75～95 quality % ethanolic solns; Raw material formaldehyde can be Paraformaldehyde 96, concentration is molten greater than the formaldehyde of 37 quality % greater than technical grade formaldehyde solution or their the composite concentration of 37 quality %.
In the preparation method of above-mentioned methylene diethyl ether, suitable catalyst levels is 0.5～5% of a reactant total mass, and optimum catalyst levels is 1～3% of a reactant total mass.
Advantage of the present invention is: adopt the immobilized acid catalyst compound probability of gac level methylene diethyl ether; This solid acid catalyst absorbent charcoal carrier is inexpensive, be easy to get; Preparation of Catalyst economy, separate easily with product, little to equipment corrosion; Spent catalyst reclaims, handles easy, is a kind of working method of new and effective, environmental protection.
Specific embodiment
The invention is further illustrated by the following examples, but be not limited to the embodiment that is lifted.
The raw material that the present invention uses is technical grade, the immobilized acid catalyst self-control of gac.Product methylene diethyl ether purity and ethanol content adopt the gas chromatograph analysis.
Instance 1
The preparation of the immobilized acid catalyst of gac: the 50g gac is cleaned oven dry, 120 ℃ of activation 2h with zero(ppm) water; Taking by weighing the pretreated gac of 30g, to be immersed in 20 times of mass concentrations be in the 60 quality % sulfuric acid, stirs down in 120 ℃ of dipping 4h, suction filtration; Washing is to neutral; 120 ℃ are dried to constant weight in baking oven, get 30g acid supported quantity after the cooling and are the immobilized acid catalyst of gac of 15 quality %, subsequent use.
Instance 2
The preparation of the immobilized acid catalyst of gac: the 50g gac is cleaned oven dry, 120 ℃ of activation 2h with zero(ppm) water; Taking by weighing the pretreated gac of 40g, to be immersed in 20 times of mass concentrations be in the 98 quality % sulfuric acid, stirs down in 120 ℃ of dipping 4h, suction filtration; Washing is to neutral; 120 ℃ are dried to constant weight in baking oven, get 40g acid supported quantity after the cooling and are the immobilized acid catalyst of gac of 22 quality %, subsequent use.
Instance 3
In the 500ml there-necked flask that TM, magnetic stirring apparatus, φ 20 * 700 packing towers and rectifying head are housed, adding concentration respectively is 37 quality % formaldehyde solution 60g, absolute ethyl alcohol 136g, the immobilized H of gac of instance 1 preparation
2SO
4Catalyzer 15.7g stir to heat up, and is in the boiling situation to the tower still, and total reflux to tower top temperature is stabilized in 74 ℃, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 ℃ of top temperature; Rise with the top temperature, progressively strengthen reflux ratio, when the top temperature reached 76 ℃, reflux ratio was increased to 4 ﹕ 1; When pushing up temperature greater than 76 ℃, control reflux ratio 1 ﹕ 1 switches to collect and pushes up temperature less than 80 ℃ of fractions, and reaction finishes, cooling.Collect methylene diethyl ether fraction 99g, gas chromatographic analysis methylene diethyl ether purity 57.8%, ethanol content 38.5%; Collect ethanol fraction 48.1g, gas chromatographic analysis methylene diethyl ether content 20.4%, ethanol content 79.0%.This thick product can make purity greater than 99% methylene diethyl ether through rectifying.
Instance 4
In the 500ml there-necked flask that TM, magnetic stirring apparatus, φ 20 * 700 packing towers and rectifying head are housed, adding concentration respectively is 60 quality % formaldehyde solution 40g, and concentration is 95 quality % ethanol 154.9g, the immobilized H of gac of instance 2 preparations
2SO
4Catalyzer 3.9g stir to heat up, and is in the boiling situation to the tower still, and total reflux to tower top temperature is stabilized in 74 ℃, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 ℃ of top temperature; Rise with the top temperature, progressively strengthen reflux ratio, when the top temperature reached 76 ℃, reflux ratio was increased to 4 ﹕ 1; When pushing up temperature greater than 76 ℃, control reflux ratio 1 ﹕ 1 switches to collect and pushes up temperature less than 80 ℃ of fractions, and reaction finishes, cooling.Collect methylene diethyl ether fraction 103.6g, gas chromatographic analysis methylene diethyl ether purity 62.1%, ethanol content 37.6%; Collect ethanol fraction 48.6g, gas chromatographic analysis methylene diethyl ether content 31.7%, ethanol content 68.3%.This thick product can make purity greater than 99% methylene diethyl ether through rectifying.
Instance 5
In the 500ml there-necked flask that TM, magnetic stirring apparatus, φ 20 * 700 packing towers and rectifying head are housed, adding concentration respectively is 50 quality % formaldehyde solution 60g, and concentration is 95 quality % ethanol 121g, the immobilized H of gac of instance 2 preparations
2SO
4Catalyzer 7.2g stir to heat up, and is in the boiling situation to the tower still, and total reflux to tower top temperature is stabilized in 74 ℃, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 ℃ of top temperature; Rise with the top temperature, progressively strengthen reflux ratio, when the top temperature reached 76 ℃, reflux ratio was increased to 4 ﹕ 1; When pushing up temperature greater than 76 ℃, control reflux ratio 1 ﹕ 1 switches to collect and pushes up temperature less than 80 ℃ of fractions, and reaction finishes, cooling.Collect methylene diethyl ether fraction 124.4g, gas chromatographic analysis methylene diethyl ether purity 69.1%, ethanol content 30.6%; Collect ethanol fraction 3.8g, gas chromatographic analysis methylene diethyl ether content 31.1%, ethanol content 68.5%.This thick product can make purity greater than 99% methylene diethyl ether through rectifying.
Instance 6
In the 500ml there-necked flask that TM, magnetic stirring apparatus, φ 20 * 700 packing towers and rectifying head are housed, adding concentration respectively is 37 quality % formaldehyde solution 70g, absolute ethyl alcohol 119g, the immobilized H of gac of instance 2 preparations
2SO
4Catalyzer 9.4g stir to heat up, and is in the boiling situation to the tower still, and total reflux to tower top temperature is stabilized in 74 ℃, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 ℃ of top temperature; Rise with the top temperature, progressively strengthen reflux ratio, when the top temperature reached 76 ℃, reflux ratio was increased to 4 ﹕ 1; When pushing up temperature greater than 76 ℃, control reflux ratio 1 ﹕ 1 switches to collect and pushes up temperature less than 80 ℃ of fractions, and reaction finishes, cooling.Collect methylene diethyl ether fraction 108.7g, gas chromatographic analysis methylene diethyl ether purity 72.3%, ethanol content 26.5%; Collect ethanol fraction 16.5g, gas chromatographic analysis methylene diethyl ether content 46.2%, ethanol content 53.3%.This thick product can make purity greater than 99% methylene diethyl ether through rectifying.
Instance 7
In the 500ml there-necked flask that TM, magnetic stirring apparatus, φ 20 * 700 packing towers and rectifying head are housed, add Paraformaldehyde 96 22g respectively, concentration is 75 quality % ethanol 170.9g, the immobilized H of gac of instance 2 preparations
2SO
4Catalyzer 11.6g stir to heat up, and is in the boiling situation to the tower still, and total reflux to tower top temperature is stabilized in 74 ℃, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 ℃ of top temperature; Rise with the top temperature, progressively strengthen reflux ratio, when the top temperature reached 76 ℃, reflux ratio was increased to 4 ﹕ 1; When pushing up temperature greater than 76 ℃, control reflux ratio 1 ﹕ 1 switches to collect and pushes up temperature less than 80 ℃ of fractions, and reaction finishes, cooling.Collect methylene diethyl ether fraction 94g, gas chromatographic analysis methylene diethyl ether purity 60.8%, ethanol content 38.6%; Collect ethanol fraction 50.5g, gas chromatographic analysis methylene diethyl ether content 19.3%, ethanol content 80.5%.This thick product can make purity greater than 99% methylene diethyl ether through rectifying.
Instance 8
Residual moisture in the instance 5 reaction back there-necked flasks is left (the immobilized H of gac
2SO
4Catalyzer is stayed in the bottle), add Paraformaldehyde 96 22g then, concentration is 75 quality % ethanol 170.9g, stir to heat up, and is in the boiling situation to the tower still, and total reflux to tower top temperature is stabilized in 74 ℃, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 ℃ of top temperature; Rise with the top temperature, progressively strengthen reflux ratio, when the top temperature reached 76 ℃, reflux ratio was increased to 4 ﹕ 1; When pushing up temperature greater than 76 ℃, control reflux ratio 1 ﹕ 1 switches to collect and pushes up temperature less than 80 ℃ of fractions, and reaction finishes, cooling.Collect methylene diethyl ether fraction 70.8g, gas chromatographic analysis methylene diethyl ether purity 62.8%, ethanol content 36.8%; Collect ethanol fraction 74g, gas chromatographic analysis methylene diethyl ether content 29.1%, ethanol content 70.8%.This thick product can make purity greater than 99% methylene diethyl ether through rectifying.
Claims (4)
1. the immobilized acid catalyst of gac prepares the methylene diethyl ether method; It is characterized in that in the reaction kettle that has whisking appliance, rectifying tower formaldehyde and ethanol are raw material, under the solid acid catalyst effect, carry out paradoxical reaction and press; Temperature of reaction is 70～100 ℃; The control reflux ratio is 1 ﹕, 1～4 ﹕ 1, at 74～76 ℃ of fractions of overhead collection, makes methylene diethyl ether; Wherein formaldehyde and alcoholic acid mole proportioning are 1 ﹕, 2～1 ﹕ 5, and raw material formaldehyde is the formaldehyde solution of concentration greater than 37 quality %, and feed ethanol is that absolute ethyl alcohol or concentration are the ethanolic soln of 75～95 quality %; Solid acid catalyst is the immobilized acid catalyst of gac, and active ingredient acid is sulfuric acid, and sour supported quantity is 15～25 quality %; The solid acid catalyst consumption is 0.3～10% of a reactant total mass.
2. the immobilized acid catalyst of gac according to claim 1 prepares the methylene diethyl ether method; The preparation method who it is characterized in that the immobilized acid catalyst of gac is: gac is cleaned oven dry, 115～125 ℃ of activation 2～4 h with zero(ppm) water; Taking by weighing a certain amount of pretreated gac, to be immersed in 25～30 times of mass concentrations be in 60～98 quality % sulphuric acid solns; Stirring refluxes in 100～140 ℃ down floods 3～5 h, suction filtration, and washing is to neutral; 115～125 ℃ are dried to constant weight in baking oven, get the immobilized acid catalyst of gac after the cooling.
3. the immobilized acid catalyst of gac according to claim 1 prepares the methylene diethyl ether method, it is characterized in that formaldehyde and alcoholic acid mole proportioning are 1 ﹕, 2.3～1 ﹕ 4, and the solid acid catalyst consumption is 0.5～5% of a reactant total mass.
4. the immobilized acid catalyst of gac according to claim 3 prepares the methylene diethyl ether method, it is characterized in that formaldehyde and alcoholic acid mole proportioning are 1 ﹕, 2.5～1 ﹕ 3, and the solid acid catalyst consumption is 1～3% of a reactant total mass.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739462A (en) * | 2013-12-31 | 2014-04-23 | 贵州黔晟新能源实业有限公司 | Preparation method of diethoxymethane |
| CN104974021A (en) * | 2015-06-29 | 2015-10-14 | 南京林业大学 | Method using sulfuric acid modified nano-level HSZM-5 catalyst to prepare bis(low-carbon alkyloxy)methane |
| CN105032473A (en) * | 2015-06-29 | 2015-11-11 | 南京林业大学 | Method for preparing formaldehydedibutylacetal by adopting sulfuric acid modified process nano-grade HZSM-5 catalyst |
| CN108047006A (en) * | 2017-12-29 | 2018-05-18 | 南京师范大学 | A kind of method for preparing diethoxymethane |
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| CN1537839A (en) * | 2003-06-30 | 2004-10-20 | 南京师范大学 | Continuous reaction rectifying synthesizing methylene diethyl ether technology |
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| CN1537839A (en) * | 2003-06-30 | 2004-10-20 | 南京师范大学 | Continuous reaction rectifying synthesizing methylene diethyl ether technology |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739462A (en) * | 2013-12-31 | 2014-04-23 | 贵州黔晟新能源实业有限公司 | Preparation method of diethoxymethane |
| CN103739462B (en) * | 2013-12-31 | 2016-03-23 | 贵州黔晟新能源实业有限公司 | A kind of preparation method of methylene diethyl ether |
| CN104974021A (en) * | 2015-06-29 | 2015-10-14 | 南京林业大学 | Method using sulfuric acid modified nano-level HSZM-5 catalyst to prepare bis(low-carbon alkyloxy)methane |
| CN105032473A (en) * | 2015-06-29 | 2015-11-11 | 南京林业大学 | Method for preparing formaldehydedibutylacetal by adopting sulfuric acid modified process nano-grade HZSM-5 catalyst |
| CN105032473B (en) * | 2015-06-29 | 2017-06-16 | 南京林业大学 | A kind of method using the sulfuric acid modified catalyst preparation dialkoxy methanes for the treatment of nanoscale HZSM 5 |
| CN108047006A (en) * | 2017-12-29 | 2018-05-18 | 南京师范大学 | A kind of method for preparing diethoxymethane |
| CN108047006B (en) * | 2017-12-29 | 2021-05-14 | 南京师范大学 | Method for preparing diethoxymethane |
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Application publication date: 20121128 Assignee: Yizheng Huana Technology Co., Ltd. Assignor: Nanjing Forestry University|Anhui Jixi Sanming Fine Chemical Co., Ltd. Contract record no.: 2014320000729 Denomination of invention: Method for preparing diethoxymethane by using active carbon supported solid acid catalyst Granted publication date: 20140730 License type: Exclusive License Record date: 20141124 |
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