CN102795976B - Method for preparing diethoxymethane by using active carbon supported solid acid catalyst - Google Patents
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- CN102795976B CN102795976B CN201110134039.9A CN201110134039A CN102795976B CN 102795976 B CN102795976 B CN 102795976B CN 201110134039 A CN201110134039 A CN 201110134039A CN 102795976 B CN102795976 B CN 102795976B
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- 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 methylene diethyl ether method; Methylene diethyl ether also claims ethylal, and structural formula is: CH
3cH
2oCH
2o CH
2cH
3; Belong to field of chemical technology.
Background technology
Methylene diethyl ether, is colourless transparent liquid, and molecular formula is C
5h
12o
2, molecular weight is 104.15,88 DEG C of sterling boiling points, and fusing point-66.50 DEG C, in 20 DEG C of water, solubleness is 9%(wt), the good character having, can be used for organic synthesis and extraction, dilution, recrystallization equal solvent.
Methylene diethyl ether is as the solvent in organic synthesis, it is a kind of protophobic solvent, very low to the avidity of water, there is water insoluble and nonhygroscopic character, therefore do not need further dry just can be directly used in some to the reaction of water sensitive as in organometallic reaction; Methylene diethyl ether viscosity is low, can make post-reaction treatment simple for low-temp reaction and the large reaction of other viscosity, 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 highly basic condition.Solvent is made in some other familiar reaction all available methylene diethyl ether, as alkylation, acylations, organolithium reaction and Grignard reaction and oxidizing reaction.
Methylene diethyl ether is as the auxiliary agents such as fuel, reaction reagent.As Equivalent, the carbonylation reaction substrate of ethoxymethyl reagent, formaldehyde, prepare phenylglycine derivatives and other amino acid, prepare ether and ester etc. as the source of ethanol.
Methylene diethyl ether main preparation methods has: acetal method, the paraxin by-product method etc. of methylene dichloride method, dimethyl sulfoxide method, Calcium Chloride Method, formaldehyde and ethanol.
Methylene dichloride method is 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 being 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 to pollution, thereby is unfavorable for scale operation.
Acetal method is under acid catalyst effect, to be reacted with ethanol by formaldehyde, and simple to operate, the reaction times is short, and yield is high, is comparatively ideal preparation method, is also the method that current investigator pays close attention to most.
In the production process of paraxin, generated by the urotropine solution of p-nitro-2-bromoacetophenone, in this solution, add the ethanolic soln of hydrochloric acid, obtain byproduct methylene diethyl ether, many production of chloramphenicol producer utilizes this method to obtain methylene diethyl ether.
The at present aldol condensation method of comparative maturity, synthesis technique adopts intermittently substantially, continuously and three kinds of operating method of catalytic distillation carry out.Classical aldol reaction uses mineral acid (as H
2sO
4, HF, H
3pO
4, tosic acid etc.) and Lewis acid (as A1C1
3, FeC1
3deng) catalyzer, all there is good catalytic activity, but there is difficult separation and recycling, to the shortcoming such as equipment corrosion is serious.People develop solid acid catalyst for this reason, as Zeo-karb, crystal aluminosilicate, HZSM-5, H
4siW
12o
40/ SiO
2heteropolyacid catalysts etc. replace liquid acid, thereby establish a kind of methylal reactive distillation novel process for suitability for industrialized production.In the using method of catalyzer; can fill loose granules of catalyst; also catalyzer can be scattered in container or reaction tower with mud form, also have catalyzer is filled together with drawing uncommon ring, somebody is placed in catalyzer in cloth bag or with filling and use after Stainless Steel Cloth parcel.
Summary of the invention
Object of the present invention provides a kind of economical in reaction, catalyzer and product separation easy, little, clean to equipment corrosion methylene diethyl ether preparation method.
Technology contents of the present invention is: the immobilized acid catalyst of a kind of gac is prepared methylene diethyl ether method, it is characterized in that in the reactor with agitator, rectifying tower, formaldehyde and ethanol are raw material, under solid acid catalyst effect, carry out paradoxical reaction pressure, temperature of reaction is 70～100 DEG C, controlling reflux ratio is 1 ﹕ 1～4 ﹕ 1, at 74～76 DEG C of fractions of overhead collection, makes methylene diethyl ether product; Filter out after the tower reactor aqueous solution, catalyzer is stayed in still and is recycled; Wherein mole proportioning of formaldehyde and ethanol is 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 %; Solid acid catalyst consumption is 0.3～10% of reactant total mass.
It is thick product that the present invention makes methylene diethyl ether, methylene diethyl ether content approximately 60～70%, and all the other are mainly second alcohol and water; Wherein methylene diethyl ether and water can form azeotrope, and the boiling point of azeotrope is 75.2 DEG C, quality content 10%, and methylene diethyl ether and ethanol can form azeotrope, and the boiling point of azeotrope is 74.2 DEG C, ethanol mass content 32%.This thick product, by refining, removes second alcohol and water wherein, can make the product that purity is greater than 99%.
The present invention develops the immobilized acid catalyst system of a kind of gac, and such catalyst preparation process is simple, by sulfuric acid by with the effect of charcoal base after become insoluble solid acid.Although such catalyzer is also by the protonic acid position (SO on it
3h) play katalysis, but due to-SO
3h and C key have formed covalent linkage, belong to hydrophobic material, and it can effectively absorb organic molecule and not absorb water.In the time having water to exist, it has been avoided protonic acid position easily hydration to occur and has reduced the problem of catalytic activity, and contributes to reactant to promote reaction to carry out with contacting of acid position.
In the preparation method of above-mentioned methylene diethyl ether, the immobilized acid catalyst of gac is taking gac as carrier, taking sulfuric acid as immobilized thing, its preparation process: gac is clean with distilled water, dry, 115～125 DEG C of activation 2～4 h, taking a certain amount of pretreated gac, to be immersed in 25～30 times of mass concentrations be in 60～98 quality % sulphuric acid solns, under stirring, reflux and flood 3～5 h in 100～140 DEG C, suction filtration, washing is to neutral, and in baking oven, 115～125 DEG C are dried to constant weight, after cooling the immobilized acid catalyst of gac.This catalyzer temperature tolerance is good, little to equipment corrosion, after reaction, gets final product and product separation through filtering, and can recycle, and 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 DEG C, and reflux ratio is corresponding increase with the increase of temperature of reaction, and suitable tower top temperature is 74～76 DEG C; Reaction finishes rear filtration, and the tower reactor aqueous solution is discharged, and solid acid catalyst is stayed in reactor and recycled; Suitable mole of proportioning of formaldehyde and ethanol is 1 ﹕ 2.2～1 ﹕ 4; Suitable mole of proportioning of formaldehyde and ethanol is 1 ﹕ 2.5～1 ﹕ 3; The increase of ethanol consumption can improve the transformation efficiency of formaldehyde, thereby improves methylene diethyl ether yield, but ethanol consumption too much can bring ethanol and methylene diethyl ether product separation problem; Feed ethanol can be dehydrated alcohol, concentration is that the ethanolic soln of 75～95 quality % or the concentration of the rear recovery of methylene diethyl ether purification are 75～95 quality % ethanolic solns; Raw material formaldehyde can be paraformaldehyde, concentration and is greater than the technical grade formaldehyde solution of 37 quality % or their composite concentration to be greater than the formaldehyde of 37 quality % molten.
In the preparation method of above-mentioned methylene diethyl ether, suitable catalyst levels is 0.5～5% of reactant total mass, and optimum catalyst levels is 1～3% of 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, catalyzer preparation is economical, easy, little to equipment corrosion with product separation, waste catalyst recovery, processing easyly, is a kind of production method of new and effective, environmental protection.
Specific embodiment
The invention is further illustrated by the following examples, but be not limited to lifted embodiment.
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 gas chromatograph analysis.
Example 1
The preparation of the immobilized acid catalyst of gac: 50g gac is clean with distilled water, dry, 120 DEG C of activation 2h, taking the pretreated gac of 30g, to be immersed in 20 times of mass concentrations be in 60 quality % sulfuric acid, under stirring in 120 DEG C of dipping 4h, suction filtration, washing is to neutral, in baking oven, 120 DEG C are dried to constant weight, after cooling 30g acid supported quantity be the immobilized acid catalyst of gac of 15 quality %, for subsequent use.
Example 2
The preparation of the immobilized acid catalyst of gac: 50g gac is clean with distilled water, dry, 120 DEG C of activation 2h, taking the pretreated gac of 40g, to be immersed in 20 times of mass concentrations be in 98 quality % sulfuric acid, under stirring in 120 DEG C of dipping 4h, suction filtration, washing is to neutral, in baking oven, 120 DEG C are dried to constant weight, after cooling 40g acid supported quantity be the immobilized acid catalyst of gac of 22 quality %, for subsequent use.
Example 3
In the 500ml there-necked flask that thermometer, magnetic stirring apparatus, φ 20 × 700 packing towers and rectifying head are housed, adding respectively concentration is 37 quality % formaldehyde solution 60g, dehydrated alcohol 136g, the immobilized H of gac prepared by example 1
2sO
4catalyzer 15.7g, stirs and heats up, and to tower reactor, in boiling situation, total reflux to tower top temperature is stabilized in 74 DEG C, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 DEG C of top temperature; Rise with top temperature, progressively strengthen reflux ratio, in the time that top temperature reaches 76 DEG C, reflux ratio is increased to 4 ﹕ 1; In the time that top temperature is greater than 76 DEG C, control reflux ratio 1 ﹕ 1, to switch collection top temperature and be less than 80 DEG C of fractions, 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 by rectifying the methylene diethyl ether that purity is greater than 99%.
Example 4
In the 500ml there-necked flask that thermometer, magnetic stirring apparatus, φ 20 × 700 packing towers and rectifying head are housed, adding respectively concentration is 60 quality % formaldehyde solution 40g, and concentration is 95 quality % ethanol 154.9g, the immobilized H of gac prepared by example 2
2sO
4catalyzer 3.9g, stirs and heats up, and to tower reactor, in boiling situation, total reflux to tower top temperature is stabilized in 74 DEG C, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 DEG C of top temperature; Rise with top temperature, progressively strengthen reflux ratio, in the time that top temperature reaches 76 DEG C, reflux ratio is increased to 4 ﹕ 1; In the time that top temperature is greater than 76 DEG C, control reflux ratio 1 ﹕ 1, to switch collection top temperature and be less than 80 DEG C of fractions, 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 by rectifying the methylene diethyl ether that purity is greater than 99%.
Example 5
In the 500ml there-necked flask that thermometer, magnetic stirring apparatus, φ 20 × 700 packing towers and rectifying head are housed, adding respectively concentration is 50 quality % formaldehyde solution 60g, and concentration is 95 quality % ethanol 121g, the immobilized H of gac prepared by example 2
2sO
4catalyzer 7.2g, stirs and heats up, and to tower reactor, in boiling situation, total reflux to tower top temperature is stabilized in 74 DEG C, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 DEG C of top temperature; Rise with top temperature, progressively strengthen reflux ratio, in the time that top temperature reaches 76 DEG C, reflux ratio is increased to 4 ﹕ 1; In the time that top temperature is greater than 76 DEG C, control reflux ratio 1 ﹕ 1, to switch collection top temperature and be less than 80 DEG C of fractions, 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 by rectifying the methylene diethyl ether that purity is greater than 99%.
Example 6
In the 500ml there-necked flask that thermometer, magnetic stirring apparatus, φ 20 × 700 packing towers and rectifying head are housed, adding respectively concentration is 37 quality % formaldehyde solution 70g, dehydrated alcohol 119g, the immobilized H of gac prepared by example 2
2sO
4catalyzer 9.4g, stirs and heats up, and to tower reactor, in boiling situation, total reflux to tower top temperature is stabilized in 74 DEG C, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 DEG C of top temperature; Rise with top temperature, progressively strengthen reflux ratio, in the time that top temperature reaches 76 DEG C, reflux ratio is increased to 4 ﹕ 1; In the time that top temperature is greater than 76 DEG C, control reflux ratio 1 ﹕ 1, to switch collection top temperature and be less than 80 DEG C of fractions, 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 by rectifying the methylene diethyl ether that purity is greater than 99%.
Example 7
In the 500ml there-necked flask that thermometer, magnetic stirring apparatus, φ 20 × 700 packing towers and rectifying head are housed, add respectively paraformaldehyde 22g, concentration is 75 quality % ethanol 170.9g, the immobilized H of gac prepared by example 2
2sO
4catalyzer 11.6g, stirs and heats up, and to tower reactor, in boiling situation, total reflux to tower top temperature is stabilized in 74 DEG C, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 DEG C of top temperature; Rise with top temperature, progressively strengthen reflux ratio, in the time that top temperature reaches 76 DEG C, reflux ratio is increased to 4 ﹕ 1; In the time that top temperature is greater than 76 DEG C, control reflux ratio 1 ﹕ 1, to switch collection top temperature and be less than 80 DEG C of fractions, 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 by rectifying the methylene diethyl ether that purity is greater than 99%.
Example 8
Example 5 is reacted in rear there-necked flask to residual moisture from (the immobilized H of gac
2sO
4catalyzer is stayed in bottle), then add paraformaldehyde 22g, concentration is 75 quality % ethanol 170.9g, stirs and heats up, and to tower reactor, in boiling situation, total reflux to tower top temperature is stabilized in 74 DEG C, and regulating reflux ratio is 1 ﹕ 1, collects the fraction of 74～76 DEG C of top temperature; Rise with top temperature, progressively strengthen reflux ratio, in the time that top temperature reaches 76 DEG C, reflux ratio is increased to 4 ﹕ 1; In the time that top temperature is greater than 76 DEG C, control reflux ratio 1 ﹕ 1, to switch collection top temperature and be less than 80 DEG C of fractions, 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 by rectifying the methylene diethyl ether that purity is greater than 99%.
Claims (3)
1. the immobilized acid catalyst of gac is prepared methylene diethyl ether method, it is characterized in that in the reactor with agitator, rectifying tower, formaldehyde and ethanol are raw material, under solid acid catalyst effect, carry out synthesis under normal pressure, temperature of reaction is 70～100 DEG C, controlling reflux ratio is 1 ﹕ 1～4 ﹕ 1, at 74～76 DEG C of fractions of overhead collection, makes methylene diethyl ether; Wherein mole proportioning of formaldehyde and ethanol is 1 ﹕ 2～1 ﹕ 5, and raw material formaldehyde is the formaldehyde solution that concentration is greater than 37 quality %, and feed ethanol is that dehydrated 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 %; Solid acid catalyst consumption is 0.3～10% of reactant total mass; The preparation method of the immobilized acid catalyst of gac is: with distilled water, gac is clean, dry, 115～125 DEG C of activation 2～4 h, taking a certain amount of pretreated gac, to be immersed in 25～30 times of mass concentrations be in 60～98 quality % sulphuric acid solns, under stirring, in 100～140 DEG C of dipping 3～5 h that reflux, suction filtration, washs to neutral, in baking oven, 115～125 DEG C are dried to constant weight, after cooling the immobilized acid catalyst of gac.
2. the immobilized acid catalyst of gac according to claim 1 is prepared methylene diethyl ether method, and mole proportioning that it is characterized in that formaldehyde and ethanol is 1 ﹕ 2.3～1 ﹕ 4, and solid acid catalyst consumption is 0.5～5% of reactant total mass.
3. the immobilized acid catalyst of gac according to claim 2 is prepared methylene diethyl ether method, and mole proportioning that it is characterized in that formaldehyde and ethanol is 1 ﹕ 2.5～1 ﹕ 3, and solid acid catalyst consumption is 1～3% of reactant total mass.
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| 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 |
| 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 |
| CN104974021B (en) * | 2015-06-29 | 2017-04-19 | 南京林业大学 | Method using sulfuric acid modified nano-level HSZM-5 catalyst to prepare bis(low-carbon alkyloxy)methane |
| CN108047006B (en) * | 2017-12-29 | 2021-05-14 | 南京师范大学 | 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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| 张士英，吴达俊.二乙氧基甲烷的制备和应用.《化学试剂》.1998,第20卷(第2期), * |
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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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