CN104387228A - Preparation method for anhydrous ethanol - Google Patents
Preparation method for anhydrous ethanol Download PDFInfo
- Publication number
- CN104387228A CN104387228A CN201410511208.XA CN201410511208A CN104387228A CN 104387228 A CN104387228 A CN 104387228A CN 201410511208 A CN201410511208 A CN 201410511208A CN 104387228 A CN104387228 A CN 104387228A
- Authority
- CN
- China
- Prior art keywords
- film
- molecular sieve
- ethanol
- mcm
- room temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method for anhydrous ethanol. Concretely, by adding modified MCM-41 into PDMS (polydimethylsiloxane), the film-forming capability and the mechanical strength of PDMS are effectively improved, the film swelling property is reduced, and the pressure bearing capability of the film is improved. Additionally, addition of modified MCM-41 helps to further improve the free volume of the film and enable the permeation rate of the film to be improved, and because modified MCM-41 contains a large amount of hydrophobic groups, the selectivity of the film is better that a film simply added with silicon dioxide and other inorganic substances. A film purification system is capable of effectively reducing water content in ethanol, and anhydrous ethanol is obtained after passing through the film system.
Description
Technical field
The invention discloses a kind of preparation method of dehydrated alcohol, concrete belongs to field of medicine and chemical technology.
Background technology
Dehydrated alcohol is a kind of achromaticity and clarification liquid.There is calcination taste.Easy flowing.Very easily from air, absorb moisture, can dissolve each other with arbitrary proportion with water and the multiple organic solvent such as chloroform, ether.Azeotropic mixture (moisture 4.43%) can be formed, azeotropic point 78.15 DEG C with water.Relative density (d204) 0.789.Fusing point-114.1 DEG C.Boiling point 78.5 DEG C.Refractive index (n20D) 1.361.Flash-point (volatilizing the air mixed near inflammable gas and liquid level in the vessel in heating of regulation structure, temperature when can be lighted by Mars when reaching finite concentration) 13 DEG C during closed-cup.Inflammable.Steam and air can form explosive mixture, limits of explosion 3.5%-8.0%(volume).
In the lab, water content 5% ethanol by with magnesium rod reflux boil altogether after obtain the dehydrated alcohol of water content less than 0.5%.Because second alcohol and water forms in the pressure of 1 standard atmosphere the azeotrope that azeotropic point is 78.1 DEG C, now in gas phase and liquid phase, the massfraction of ethanol is all 95.6%, therefore use common rectificating method can not obtain moisture lower than 5% dehydrated alcohol.In existing Industrial Production of Anhydrous Alcohol technology, divide by character and mainly contain three major types method:
The first kind is rectification method, concrete has azeotropic distillation, salt distillation, rectification under vacuum, the essence of these methods is all by adding three components or changing air pressure, thus destruction ethanol content is the azeotrope of 95.6%, makes the relative content of ethanol be increased to more than 99.5%, thus reaches the object preparing dehydrated alcohol; In industry component distillation, be water entrainer with benzene, toluene, cyclohexane give, ternary low-boiling-point substance is formed with ethanol, dehydrated alcohol is obtained after being taken out of from system by water, salt distillation is then the salts solution adding high density, such as Potassium ethanoate, sodium-acetate etc., in order to change the saturated vapor pressure of water or ethanol, thus destruction azeotrope, ethanol is steamed.These methods need interpolation the 3rd material to enter in system, and the especially interpolation of the strong carcinogen such as benzene, hexanaphthene and high concentration salt solutions, environmental pollution is serious.Rectification under vacuum is high to equipment requirements, and power consumption is large simultaneously.
Equations of The Second Kind is chemical method, is particularly added in 95% ethanol by different sorts water-removal agent, and water generation chemical reaction wherein forms other materials, thus destroys azeotrope, and the water-removal agent added can be unslaked lime, hydrolith or sodium hydride etc.; The defect of chemical method is, add the 3rd material and enter in system, simultaneous reactions can produce extra gas or insoluble substance, and these have certain impact or corrosion to production unit, is unfavorable for clean maintenance.Meanwhile, dewater reaction not exclusively with unslaked lime, and hydrolith or sodium hydride cost too high, and it is dangerous to generate hydrogen.
3rd class is absorption method, particularly different types of water-retaining agent is added in 95% ethanol, by adsorption, the water of the inside is removed, again by water-retaining agent and separation of ethanol, conventional water-retaining agent has molecular sieve, biological material and hydroscopic high-molecular resin material etc., especially biological material, because it is nontoxic, becomes the hot fields that current research prepares anhydrous organic solvent.
4th class is film pervasion evaporation method (Pervaporation, PV), specifically by the film of the unlike material difference to water and dissolve with ethanol degree and diffusibleness, to a kind of technology that second alcohol and water is separated.According to the selectivity of film, we can be divided into preferential water permeable membrane and the large class of ethanol-permselective membrane two.The material of film mainly comprises polyimide (PI), polyvinyl alcohol (PVA), rhodia (CA), dimethione (PDMS), polysulfones (PS), polycarbonate (PC) etc.Wherein preferential water permeable membrane is mostly for the enrichment of low-concentration ethanol, and ethanol-permselective membrane then tries out the production in high concentration ethanol.The method energy consumption is low, it is little to pollute, and is a kind of technique of environmental protection.102294182
Dimethione (PDMS) is a kind of rubbery feel polymer of straight-chain.Si-O-Si bond angle change in PDMS, between 130 ° ~ 160 °, makes its molecular chain high crimp and helically structure.Each spiral is made up of the silica chain link of about 6, and nonpolar methyl is outside, plays shielding effect.Such structure makes the Interaction Force of silica chain little, and molecular volume is large, and surface tension is little.Thus PDMS is had the good avidity of organism and hydrophobicity.
The separation factor of film: α=Y
a* X
b/ Y
b* X
a, wherein, subscript A is preferential through component, Y
awith Y
brepresent massfraction respective in penetrant, X
awith X
brepresentative massfraction before separation.
The people such as Jiang Guanjin report the film pervasion evaporation production line that Shandong Megavision Membrane Technology & Engineering Co., Ltd.'s existing a set of year treatment capacity reaches 40,000 t/a.But do not find relevant technical parameter.Patent 201310256342.5 discloses preparation method and the application of the silane-modified mesopore molecular sieve of a kind of nitrogen/PDMS hybridization compounding film.Modified MCM-41 mesopore molecular sieve/PDMS the composite membrane announced in patent is used to be separated alcohol/water, n-butanol/water system.The data announced in patent, this film is 9.44 to the best result of massfraction 5% alcohol/aqueous systems from the factor, far below the separation factor 68.75 of n-butanol/water, obtains the ethanol of 32.9% according to separation factor after calculating its purifying.
Although PDMS has been proved to be as the very high organic permselective membrane material of permeation flux, its separation performance has still had larger room for promotion, and filling may be a kind of easy, practical membrane modifying means.Current research rests on inorganics filled film more, is not that a lot, main weighting materials has cyclodextrin, silica gel etc. to the report of organism filling film.Know by inference according to the similar principle that mixes in mould material selection gist, organic filling is applicable equally, and be expected to obtain more inorganics filled better effect, by known to the analysis of cyclodextrin physical property, the inclusion property of cyclodextrin to guest molecule determines its distinctive adsorption selectivity to organic molecule.
Summary of the invention
The present invention puies forward the method that a kind of modified membrane by PDMS much of for preparing dehydrated alcohol, and the MCM-41 adding modification in PDMS can effectively improve its film forming ability and physical strength, reduces the swelling property of film, improves the ability to bear of film to pressure.
The present invention seeks to be realized by following scheme:
A kind of anhydrous ethanol preparation method, comprise the MCM-41 molecular sieve of modification, Modified MCM-41 molecular sieve and dimethione and mix the preparation of poly-purification membrane, step with the film prepared purifying ethanol in separation system, it is characterized in that, by the purification membrane that dimethione is the loaded modified MCM-41 molecular sieve of parent, in separation system ethanol at a certain temperature with cross film purification when certain vacuum tightness and obtain dehydrated alcohol.
The MCM-41 of described modification can be prepared by the following method: be dissolved in by 4-methylbenzylphosphonic acid diethyl ester in dry methylene dichloride, then add Me
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, products obtained therefrom adds in the aqueous solution in the MCM-41 molecular sieve prepared, and at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The preparation of described hybrid films can be undertaken by following methods: with the PDMS solution of normal heptane preparation massfraction 10%, more successively adding a certain amount of linking agent tetraethoxy and catalyzer dibutyl tin dilaurate wherein, making it mix by stirring; Then above-mentioned Modified MCM-41 molecular sieve is added in above-mentioned solution in proportion, fully stir, make it mix completely, be so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.
The purifies and separates of described ethanol can be undertaken by following methods: be installed in purification system by modified PDMS film obtained by above-mentioned steps.Separation and purification is carried out to the ethanol that content is 95%.The temperature of feed liquid controls at 30 ~ 45 DEG C, and the vacuum tightness of multilayer film filter system lower floor should control at 0.10 ~ 0.30MPa.
The beneficial effect of the present invention program is, can the free volume further promoted in film the transmitance of film be made to increase by the MCM-41 adding modification, containing a large amount of hydrophobic groupings in the MCM-41 of modification, the selectivity of film is compared and simply adds the effective of the inorganic substance such as silicon-dioxide, and the cyclodextrin that compares, few to the reservation of substrate.Pervaporation membrane is to ethanol/water system purifying, low concentration feed liquid is concentrated easier, and along with the massfraction in ethanol, to improve its purification more difficult, ethanol all can only be carried out one and slightly purify by present Pervaporation membrane, concentrate from a lower concentration, along with the raising of alcohol concn, the moisture content in its feed liquid is extremely difficult to be removed, and reason is that the content of water is few and can be miscible with arbitrary ratio between ethanol and water.Although can pass through repetitive operation, the accumulative concentration improving ethanol, this method energy consumption is large, equipment volume is large, the production cycle is long.It is dehydrated alcohol by ethanol purification that Pervaporation membrane of the present invention once can cross film, shortens the production cycle, reduces equipment cost, decreases energy consumption.
Embodiment
embodiment 1
The 4-methylbenzylphosphonic acid diethyl ester of 3g is dissolved in the methylene dichloride of dry 50ml, then adds the Me of 15g
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, takes in the aqueous solution that products obtained therefrom 1g adds in the MCM-41 molecular sieve of the 3g prepared, at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The PDMS of 20g being joined in 25ml normal heptane, more successively adds the linking agent tetraethoxy of 0.5g and the catalyzer dibutyl tin dilaurate of 0.2g wherein, making it mix by stirring; Then add in above-mentioned solution by above-mentioned Modified MCM-41 molecular sieve 2.0g, fully ultrasonic, stirring, makes it mix completely, is so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.Film obtained by present method is separated the ethanol-water solution of 95.5% in separation system, feed temperature be 40 DEG C, vacuum tightness is 0.15MPa, its permeation flux is 306.5g/m
2* h, separation factor is 13.5, institute's producing and ethanol concentration>=99.95%.
embodiment 2
The 4-methylbenzylphosphonic acid diethyl ester of 3g is dissolved in the methylene dichloride of dry 50ml, then adds the Me of 15g
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, takes in the aqueous solution that products obtained therefrom 1g adds in the MCM-41 molecular sieve of the 0.6g prepared, at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The PDMS of 20g being joined in 25ml normal heptane, more successively adds the linking agent tetraethoxy of 0.5g and the catalyzer dibutyl tin dilaurate of 0.2g wherein, making it mix by stirring; Then add in above-mentioned solution by above-mentioned Modified MCM-41 molecular sieve 0.6g, fully ultrasonic, stirring, makes it mix completely, is so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.Be separated the ethanol-water solution of 95.5% in film separating system obtained by present method, feed temperature be 40 DEG C, vacuum tightness is 0.15MPa, its permeation flux is 296.8g/m
2* h, separation factor is 10.5, institute's producing and ethanol concentration>=99.95%.
embodiment 3
The 4-methylbenzylphosphonic acid diethyl ester of 3g is dissolved in the methylene dichloride of dry 50ml, then adds the Me of 15g
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, takes in the aqueous solution that products obtained therefrom 1g adds in the MCM-41 molecular sieve of the 0.6g prepared, at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The PDMS of 20g being joined in 25ml normal heptane, more successively adds the linking agent tetraethoxy of 0.5g and the catalyzer dibutyl tin dilaurate of 0.2g wherein, making it mix by stirring; Then add in above-mentioned solution by above-mentioned Modified MCM-41 molecular sieve 1.6g, fully ultrasonic, stirring, makes it mix completely, is so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.Be separated the ethanol-water solution of 95.5% in film separating system obtained by present method, feed temperature be 40 DEG C, vacuum tightness is 0.15MPa, its permeation flux is 346.3g/m
2* h, separation factor is 15.5, institute's producing and ethanol concentration>=99.95%.
embodiment 4
The 4-methylbenzylphosphonic acid diethyl ester of 3g is dissolved in the methylene dichloride of dry 50ml, then adds the Me of 15g
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, takes in the aqueous solution that products obtained therefrom 1g adds in the MCM-41 molecular sieve of the 0.6g prepared, at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The PDMS of 20g being joined in 25ml normal heptane, more successively adds the linking agent tetraethoxy of 0.5g and the catalyzer dibutyl tin dilaurate of 0.2g wherein, making it mix by stirring; Then add in above-mentioned solution by above-mentioned Modified MCM-41 molecular sieve 1.6g, fully ultrasonic, stirring, makes it mix completely, is so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.Film obtained by present method is separated the ethanol-water solution of 95.5% in separation system, feed temperature be 40 DEG C, vacuum tightness is 0.15MPa, its permeation flux is 346.8g/m
2* h, separation factor is 15.5, institute's producing and ethanol concentration>=99.95%.
embodiment 5
The 4-methylbenzylphosphonic acid diethyl ester of 3g is dissolved in the methylene dichloride of dry 50ml, then adds the Me of 15g
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, takes in the aqueous solution that products obtained therefrom 1g adds in the MCM-41 molecular sieve of the 0.6g prepared, at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The PDMS of 20g being joined in 25ml normal heptane, more successively adds the linking agent tetraethoxy of 0.5g and the catalyzer dibutyl tin dilaurate of 0.2g wherein, making it mix by stirring; Then add in above-mentioned solution by above-mentioned Modified MCM-41 molecular sieve 1.6g, fully ultrasonic, stirring, makes it mix completely, is so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.Film obtained by present method is separated the ethanol-water solution of 95.5% in separation system, feed temperature be 30 DEG C, vacuum tightness is 0.15MPa, its permeation flux is 338.4g/m
2* h, separation factor is 15.5, institute's producing and ethanol concentration>=99.95%.
embodiment 6
The 4-methylbenzylphosphonic acid diethyl ester of 3g is dissolved in the methylene dichloride of dry 50ml, then adds the Me of 15g
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, takes in the aqueous solution that products obtained therefrom 1g adds in the MCM-41 molecular sieve of the 0.6g prepared, at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The PDMS of 20g being joined in 25ml normal heptane, more successively adds the linking agent tetraethoxy of 0.5g and the catalyzer dibutyl tin dilaurate of 0.2g wherein, making it mix by stirring; Then add in above-mentioned solution by above-mentioned Modified MCM-41 molecular sieve 1.6g, fully ultrasonic, stirring, makes it mix completely, is so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.Film obtained by present method is separated the ethanol-water solution of 95.5% in separation system, feed temperature be 30 DEG C, vacuum tightness is 0.15MPa, its permeation flux is 311.2g/m
2* h, separation factor is 12.8, institute's producing and ethanol concentration>=99.95%.
embodiment 7
The 4-methylbenzylphosphonic acid diethyl ester of 3g is dissolved in the methylene dichloride of dry 50ml, then adds the Me of 15g
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, takes in the aqueous solution that products obtained therefrom 1g adds in the MCM-41 molecular sieve of the 0.6g prepared, at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The PDMS of 20g being joined in 25ml normal heptane, more successively adds the linking agent tetraethoxy of 0.5g and the catalyzer dibutyl tin dilaurate of 0.2g wherein, making it mix by stirring; Then add in above-mentioned solution by above-mentioned Modified MCM-41 molecular sieve 1.6g, fully ultrasonic, stirring, makes it mix completely, is so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.Film obtained by present method is separated the ethanol-water solution of 95.5% in separation system, feed temperature be 30 DEG C, vacuum tightness is 0.1MPa, its permeation flux is 306.5g/m
2* h, separation factor is 15.8, institute's producing and ethanol concentration>=99.95%.
embodiment 8
The 4-methylbenzylphosphonic acid diethyl ester of 3g is dissolved in the methylene dichloride of dry 50ml, then adds the Me of 15g
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, takes in the aqueous solution that products obtained therefrom 1g adds in the MCM-41 molecular sieve of the 0.6g prepared, at room temperature stirs 20h, filters.Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified.Product is vacuum-drying 10 h at 50 DEG C.
The PDMS of 20g being joined in 25ml normal heptane, more successively adds the linking agent tetraethoxy of 0.5g and the catalyzer dibutyl tin dilaurate of 0.2g wherein, making it mix by stirring; Then add in above-mentioned solution by above-mentioned Modified MCM-41 molecular sieve 1.6g, fully ultrasonic, stirring, makes it mix completely, is so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.Film obtained by present method is separated the ethanol-water solution of 95.5% in separation system, feed temperature be 30 DEG C, vacuum tightness is 0.3MPa, its permeation flux is 356.5g/m
2* h, separation factor is 13.2, institute's producing and ethanol concentration>=99.95%.
Claims (7)
1. an anhydrous ethanol preparation method, it is characterized in that, by the purification membrane that dimethione is the loaded modified MCM-41 molecular sieve of parent, in separation system ethanol at a certain temperature with cross film purification when certain vacuum tightness and obtain dehydrated alcohol, wherein said preparation method also comprises the MCM-41 molecular sieve of modification and Modified MCM-41 molecular sieve and dimethione and mixes poly-purification membrane preparation.
2. according to the method described in claim 1, it is characterized in that, described dimethione is that in the purification membrane of the loaded modified MCM-41 molecular sieve of parent, the MCM-41 molecular sieve of modification and dimethione mass ratio are the MCM-41 molecular sieve of modification: 3-15 part, dimethione: 85-97 part.
3. according to the method described in claim 1, it is characterized in that, the temperature crossing film of ethanol should control at 30 ~ 45 DEG C.
4. according to the method described in claim 1, it is characterized in that, the vacuum tightness to opposite side when film crossed by ethanol is 0.10 ~ 0.30MPa.
5. according to the method described in claim 1, it is characterized in that, the MCM-41 of described modification can be prepared by the following method: be dissolved in by 4-methylbenzylphosphonic acid diethyl ester in dry methylene dichloride, then add Me
3siBr, revolves after at room temperature reacting 24 h and steams the excessive Me of removing
3siBr and methylene dichloride, solid is dissolved in MeOH revolving after stirring at room temperature 3 h and steams except MeOH, a small amount of CH of residue
2cl
2washing, products obtained therefrom adds in the aqueous solution in the MCM-41 molecular sieve prepared, and at room temperature stirs 20h, filters; Filter cake distilled water repeatedly rinses to filtrate is not luminous under ultraviolet lamp, obtains the molecular sieve through organic matter modified; Product is vacuum-drying 10 h at 50 DEG C.
6. according to the method described in claim 1, it is characterized in that, the preparation that described dimethione mixes poly-purification membrane can be undertaken by following methods: with the PDMS solution of normal heptane preparation massfraction 10%, successively adding a certain amount of linking agent tetraethoxy and catalyzer dibutyl tin dilaurate wherein again, making it mix by stirring; Then above-mentioned Modified MCM-41 molecular sieve is added in above-mentioned solution in proportion, fully stir, make it mix completely, be so namely mixed with the film-casting liquid of filling film; With scraper on poly (methyl methacrylate) plate by film-casting liquid striking film forming, room temperature places 24 h, solvent evaporation inversion of phases film forming, then at 120 DEG C dry 12h.
7. according to the method described in claim 1, it is characterized in that, described ethanol is selected from the ethanol that content is 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410511208.XA CN104387228B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of dehydrated alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410511208.XA CN104387228B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of dehydrated alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104387228A true CN104387228A (en) | 2015-03-04 |
| CN104387228B CN104387228B (en) | 2016-02-17 |
Family
ID=52605207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410511208.XA Active CN104387228B (en) | 2014-09-29 | 2014-09-29 | A kind of preparation method of dehydrated alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104387228B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548253A (en) * | 2020-05-15 | 2020-08-18 | 山东飞扬化工有限公司 | Process for producing absolute ethyl alcohol by membrane separation |
| CN116730802A (en) * | 2023-08-09 | 2023-09-12 | 潍坊中汇化工有限公司 | Preparation method of high-purity ethanol |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070031954A1 (en) * | 2005-08-03 | 2007-02-08 | Membrane Technololgy And Research, Inc. | Ethanol recovery process |
| CN1915815A (en) * | 2005-08-18 | 2007-02-21 | 北京服装学院 | Modified MCM-41 molecular sieve, and modified method |
| US20090114089A1 (en) * | 2007-11-02 | 2009-05-07 | Chunqing Liu | Microporous Aluminophosphate Molecular Sieve Membranes for Highly Selective Separations |
| CN101518719A (en) * | 2008-02-29 | 2009-09-02 | 中国科学院过程工程研究所 | Method for preparing organic-inorganic hybrid evaporation alcohol permselective membrane |
| JP2011183378A (en) * | 2010-02-09 | 2011-09-22 | Research Institute Of Innovative Technology For The Earth | New alcohol separation membrane, method for manufacturing the same, and alcohol treatment method using the same |
| CN102294182A (en) * | 2011-07-18 | 2011-12-28 | 清华大学 | Preparation method of hydrophobic nano mesoporous molecular sieve filling PDMC composite film |
| CN103349923A (en) * | 2013-06-25 | 2013-10-16 | 北京工业大学 | Preparation method and application of silazane modified mesoporous molecular sieve/PDMS (polydimethylsiloxane) hybridized composite membrane |
-
2014
- 2014-09-29 CN CN201410511208.XA patent/CN104387228B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070031954A1 (en) * | 2005-08-03 | 2007-02-08 | Membrane Technololgy And Research, Inc. | Ethanol recovery process |
| CN1915815A (en) * | 2005-08-18 | 2007-02-21 | 北京服装学院 | Modified MCM-41 molecular sieve, and modified method |
| US20090114089A1 (en) * | 2007-11-02 | 2009-05-07 | Chunqing Liu | Microporous Aluminophosphate Molecular Sieve Membranes for Highly Selective Separations |
| CN101518719A (en) * | 2008-02-29 | 2009-09-02 | 中国科学院过程工程研究所 | Method for preparing organic-inorganic hybrid evaporation alcohol permselective membrane |
| JP2011183378A (en) * | 2010-02-09 | 2011-09-22 | Research Institute Of Innovative Technology For The Earth | New alcohol separation membrane, method for manufacturing the same, and alcohol treatment method using the same |
| CN102294182A (en) * | 2011-07-18 | 2011-12-28 | 清华大学 | Preparation method of hydrophobic nano mesoporous molecular sieve filling PDMC composite film |
| CN103349923A (en) * | 2013-06-25 | 2013-10-16 | 北京工业大学 | Preparation method and application of silazane modified mesoporous molecular sieve/PDMS (polydimethylsiloxane) hybridized composite membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548253A (en) * | 2020-05-15 | 2020-08-18 | 山东飞扬化工有限公司 | Process for producing absolute ethyl alcohol by membrane separation |
| CN116730802A (en) * | 2023-08-09 | 2023-09-12 | 潍坊中汇化工有限公司 | Preparation method of high-purity ethanol |
| CN116730802B (en) * | 2023-08-09 | 2023-10-24 | 潍坊中汇化工有限公司 | Preparation method of high-purity ethanol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104387228B (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Pervaporation purification of ethylene glycol using the highly permeable PIM-1 membrane | |
| Unlu et al. | Pervaporation catalytic membrane reactor study for the production of ethyl acetate using Zr (SO4) 2. 4H2O coated chitosan membrane | |
| US10377689B2 (en) | Process for preparing polyoxymethylene dimethyl ethers from formaldehyde and methanol in aqueous solutions | |
| Li et al. | Sorption and pervaporation study of methanol/dimethyl carbonate mixture with poly (etheretherketone)(PEEK-WC) membrane | |
| Dmitrenko et al. | Development and investigation of mixed-matrix PVA-fullerenol membranes for acetic acid dehydration by pervaporation | |
| Mahmood et al. | Water–methanol separation characteristics of annealed SA/PVA complex membranes | |
| Hoshi et al. | Separation of aqueous phenol through polyurethane membranes by pervaporation | |
| CN104387228B (en) | A kind of preparation method of dehydrated alcohol | |
| Sato et al. | Enhanced production of butyl acetate via methanol-extracting transesterification membrane reactors using organosilica membrane: Experiment and modeling | |
| Unlu | High-efficiency pervaporative separation of fuel bioadditive methylal from methanol by poly (vinyl alcohol)/poly (vinylpyrrolidone) blend membrane | |
| Toth et al. | Membrane flash index: powerful and perspicuous help for efficient separation system design | |
| Doosti et al. | Polyethyleneglycol-modified cellulose acetate membrane for efficient olefin/paraffin separation | |
| CN101816897A (en) | ZSM-5 molecular sieve filled silicon rubber/cellulose acetate composite membrane and preparation method thereof | |
| Xin et al. | Highly efficient removal of cadmium (II) ions using cellulose-based monolith with a hierarchically porous structure fabricated through phase separation method | |
| Jiang et al. | Polyimide/Ionic Liquids Hybrid Membranes with NH3-Philic Channels for Ammonia-Based CO2 Separation Processes | |
| JP5113854B2 (en) | Method of absorbing methyl acrolein with ionic liquid | |
| CN101450898B (en) | UV photo-curing monomer clean production process through coupling reactor and simulated moving bed | |
| Moulik et al. | Enrichment of hydrazine from aqueous solutions by vacuum membrane distillation through microporous polystyrene membranes of enhanced hydrophobicity | |
| Baluk et al. | A new strategy for PET depolymerization: Application of bimetallic MOF-74 as a selective catalyst | |
| Toth et al. | Selection between separation alternatives: Membrane flash index (MFLI) | |
| CN104387227B (en) | A kind of preparation method of medicinal alcohol | |
| CN100402476C (en) | Method of separating 1,2-dichloropropane with DD mixture | |
| Faizal et al. | Tocopherol‐targeted membrane adsorbents prepared by hybrid molecular imprinting | |
| CN100549068C (en) | Utilize the method for cyclodextrin separating and purifying different end group polymer | |
| Chendake et al. | Transport of organic acids through polybenzimidazole based membranes by ‘Chemodialysis’ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |