CN101229491B - Method of preparing pervaporation film preferentially penetrating methyl carbonate - Google Patents
Method of preparing pervaporation film preferentially penetrating methyl carbonate Download PDFInfo
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- CN101229491B CN101229491B CN2007101767542A CN200710176754A CN101229491B CN 101229491 B CN101229491 B CN 101229491B CN 2007101767542 A CN2007101767542 A CN 2007101767542A CN 200710176754 A CN200710176754 A CN 200710176754A CN 101229491 B CN101229491 B CN 101229491B
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Abstract
The invention discloses a preparation method of two uniform membranes which first permeates the dimethyl carbonate to separate dimethyl or carbonate from methanol - dimethyl carbonate azeotrope. The invention pertains to the preparation field of chemical materials, in particular to a preparation method of pervaporation membrane through which methyl carbonate can firstly permeats to realize the separation of the dimethyl carbonate from the methanol - dimethyl carbonate azeotrope in pervaporation method. Sulphurated siliastic, solvent, linking agent and catalyst are evenly mixed by mass ratio; the mixed membrane liquid is scraped on a base plate to make uniform membranes of dimethyl polysiloxane or added with zeolite to prepare the uniform membrane of zeolite filling dimethyl polysiloxane. In particular, the two uniform membranes can be firstly removed of dimethyl carbonate during the process of pervaporation, which has good separating property. With simple technology and low cost of materials the invention obtains the uniform membranes which can permeate methyl carbonate and have good separating property.
Description
Technical field
The invention belongs to the technology of preparing of chemical materials, particularly in order to realize a kind of preferential infiltration evaporation membrane preparation method of dimethyl carbonate thoroughly of infiltration evaporation method separation of methanol/dimethyl carbonate azeotropic liquid.Especially dimethyl silicone polymer of the present invention all makes film and zeolite filling dimethyl silicone polymer is all made film, preferentially removes dimethyl carbonate in the infiltration evaporation process, shows separating property preferably.
Background technology:
Dimethyl carbonate (DMC), molecular formula are CO (OCH
3)
2, contain multiple functional groups such as methyl, methoxyl group, carbonyl methoxyl group and carbonyl in its molecular structure, thereby have good chemical reactivity.DMC is described as the novel industrial chemicals of environmental friendliness characteristic because of its hypotoxicity.In recent years, the commercial Application of DMC at home and abroad draws attention, and is obtaining swift and violent development.Reactions such as DMC can substitute severe toxicity such as phosgene, dimethyl suflfate, chloromethanes and methylchloroformate at numerous areas or carcinogenic substance carries out carbonylation, methylates, esterification and ester exchange generate multiple fine chemicals, are important organic synthesis intermediate and initiation materials; Because it has good dissolubility, can be used as senior solvent and cleaning agent, is widely used in fields such as coating, medicine, batteries; Also can be used as gasoline additive, improve the octane number and the oxygen content of gasoline, improve efficiency of combustion, reduce tail gas pollution.What the industrial production of DMC obtained is the mixture of methyl alcohol (MeOH) and dimethyl carbonate.MeOH and DMC form azeotropic liquid (MeOH wt.70%, DMC 30wt.%) under the normal pressure, and azeotropic temperature is 64 ℃.Therefore separating recovery DMC from azeotropic liquid is requisite process in the DMC industrial production.At present, the separation method of MeOH/DMC azeotropic liquid mainly contains the crystallizing process under low temperature, absorption method, extraction fractional distillation, azeotropic distillation, compression rectification method and membrane separation process.Than other several separation methods, membrane separation process has advantages such as energy consumption is low, efficient is high, the operating condition requirement is lower.
Infiltration evaporation (Pervaporation is called for short PV) has another name called pervaporation or pervaporation, is a kind of new membrane process that each component is dissolved in dense film in the liquid mixture, diffusion is different and make it to separate of utilizing.It can be used for the separation of different liquids mixture, has obtained extensive use in industry such as chemical industry, pharmacy, food.It is specially adapted to, and the way of distillation is difficult to separate or the separation of indissociable nearly boiling point, constant boiling point mixture and isomer; To minor amount of water in organic solvent and the mixed solvent remove and waste water in the separation of a small amount of organic pollution have advantage significantly technical and economically; Can also reaction product constantly be removed with biology and chemical reaction coupling, reaction conversion ratio is obviously improved.Along with the appearance of new diffusion barrier and membrane separator, the infiltration evaporation isolation technics will obtain bigger development.
Mainly contain two in order to the performance of weighing infiltrating and vaporizing membrane, i.e. the permeation flux of film and selectivity.
1) permeation flux, its definition is:
In the formula, M is the penetrating fluid quality that penetrates film; A is a membrane area, m
2T is the operating time, h; J is a permeation flux, kg/ (m
2H).
2) separation factor alpha, its definition is:
In the formula, A represents the penetrated preferably component; Y
AWith Y
BBe respectively the molar fraction of A and two kinds of components of B in penetrant; X
AWith X
BBe respectively the molar fraction of A and two kinds of components of B in the feed liquid.
Summary of the invention
The infiltration evaporation membrane preparation method that the purpose of this invention is to provide a kind of preferential saturating dimethyl carbonate.It is characterized in that this method comprises that dimethyl silicone polymer is all made film and zeolite is filled the preparation method that dimethyl silicone polymer is all made the infiltrating and vaporizing membrane of two kinds of preferential saturating dimethyl carbonates of film,
Described dimethyl silicone polymer is all made membrane preparation method: is 1: 2: 0.1～0.5: 0.06 mixing and stirring with solvent, crosslinking agent and catalyst by mass ratio with room temperature vulcanized silicone rubber (107 glue, 108 glue, 201 glue etc.), and the film liquid that is mixed with is scraped to make on substrate and all made film; At room temperature place 24h, solvent is fully volatilized, the sulfuration film forming, thickness is 120 ± 5 microns.
Described zeolite is filled dimethyl silicone polymer and is all made membrane preparation method and be: with room temperature vulcanized silicone rubber, solvent and zeolite through stir and ultrasonic mixing after, in above-mentioned mixed liquor, add crosslinking agent and catalyst, and stir, be mixed into preparation liquid, wherein the mass ratio of sulphurated siliastic and solvent, crosslinking agent, catalyst is 1: 2: 0.3: 0.06; The zeolite loading is 10～40wt.% of total amount; On substrate, scrape to make and all make film, at room temperature place 24h, solvent is fully volatilized, the sulfuration film forming, thickness is 120 ± 5 microns.
Described sulphurated siliastic is 107 glue, 108 glue or 201 glue.
Described solvent is n-hexane, normal heptane or n-decane.
Described crosslinking agent is ethyl orthosilicate, MTES or vinyltrimethoxy silane.
Described catalyst is a dibutyl tin laurate.
Described zeolite is ZSM-5 type, NU-1 type or EU-1 type.
In the laboratory, adopt performance evaluating apparatus to measure separation factor and permeation flux; The side that sees through the film device adopts the method that vacuumizes to keep infiltration component low pressure, and pressure maintains about 200Pa.The condensation of per-meate side steam is collected the back and is calculated separation factor with its each constituent mass mark of gas chromatographic analysis, and permeation flux calculates with weight method.
The invention has the beneficial effects as follows the infiltrating and vaporizing membrane that to realize that methyl alcohol/dimethyl carbonate azeotropic liquid separates, and under the different operating temperature, measure the separating property of film.
The specific embodiment
The invention provides a kind of infiltration evaporation membrane preparation method of preferential saturating dimethyl carbonate.This method comprises that dimethyl silicone polymer is all made film and zeolite is filled the preparation method that dimethyl silicone polymer is all made the infiltrating and vaporizing membrane of two kinds of preferential saturating dimethyl carbonates of film.Enumerating embodiment is below illustrated.
Embodiment 1
In the mixing and stirring of ratio shown in the table 1, the film liquid that is mixed with is scraped to make on substrate and is all made film with 107 glue and solvent normal heptane, ethyl orthosilicate, dibutyl tin laurate.At room temperature place 24h, solvent is fully volatilized, the sulfuration film forming, thickness is 120 ± 5 microns, and the dimethyl silicone polymer that makes is all made film and is measured its separating property with performance evaluating apparatus, and feed liquid is that the DMC mass fraction is 30% for the MeOH/DMC azeotropic liquid.Separating property under 40 ℃ sees Table 1.
Embodiment 2
107 glue, normal heptane and ZSM-5 type zeolite after stirring and ultrasonic mixing, are added ethyl orthosilicate and dibutyl tin laurate, and stir in above-mentioned mixed liquor.(mass ratio of 107 glue and normal heptane, ethyl orthosilicate, dibutyl tin laurate is 1: 2: 0.3 to the preparation liquid that mixes: 0.06, ZSM-5 type zeolite loading is 10～40wt.%) to scrape to make on substrate and all make film, at room temperature place 24h, solvent is fully volatilized, the sulfuration film forming, thickness is 120 ± 5 microns.The zeolite filling dimethyl silicone polymer that makes is all made film and is measured its separating property with performance evaluating apparatus, and feed liquid is that the DMC mass fraction is 30% for the MeOH/DMC azeotropic liquid.Separating property under 40 ℃ sees Table 2.
The dimethyl silicone polymer of the different ethyl orthosilicate content of table 1 is all made membrane separating property
| 107 glue: ethyl orthosilicate (mass ratio) | DMC wt.% is surveyed in infiltration | Separation factor alpha | Permeation flux J (kg/m 2·h) |
| 1∶0.1 | 56.1 | 2.98 | 1.87 |
| 1∶0.2 | 57.8 | 3.20 | 1.62 |
| 1∶0.3 | 59.7 | 3.46 | 1.41 |
| 1∶0.4 | 58.3 | 3.26 | 1.26 |
| 1∶0.5 | 56.9 | 3.08 | 1.15 |
The dimethyl silicone polymer of table 2 different zeolites loading is all made membrane separating property
| Zeolite loading (wt.%) | DMC wt.% is surveyed in infiltration | Separation factor alpha | Permeation flux J (kg/m 2·h) |
| 0 (embodiment 1) | 59.7 | 3.46 | 1.41 |
| 10 | 60.3 | 3.54 | 1.30 |
| 20 | 61.0 | 3.65 | 1.19 |
| 30 | 62.4 | 3.87 | 1.10 |
| 40 | 63.7 | 4.09 | 1.05 |
Embodiment 3
107 glue and solvent normal heptane, ethyl orthosilicate, dibutyl tin laurate were pressed 1: 2: 0.3: 0.06 (mass ratio) mixing and stirring, the film liquid that is mixed with are scraped to make on substrate and are all made film.At room temperature place 24h, solvent is fully volatilized, the sulfuration film forming, thickness is 120 ± 5 microns.The dimethyl silicone polymer that makes is all made film and is measured its separating property with performance evaluating apparatus, and feed liquid is that the DMC mass fraction is 30% for the MeOH/DMC azeotropic liquid.Separating property under the different temperatures sees Table 3.
Embodiment 4
107 glue, normal heptane and ZSM-5 type zeolite after stirring and ultrasonic mixing, are added ethyl orthosilicate and dibutyl tin laurate, and stir in above-mentioned mixed liquor.(mass ratio of 107 glue and normal heptane, ethyl orthosilicate, dibutyl tin laurate is 1: 2: 0.3 to the preparation liquid that mixes: 0.06, ZSM-5 type zeolite loading is 40wt.%) on substrate, scrape to make and all make film, at room temperature place 24h, solvent is fully volatilized, the sulfuration film forming, thickness is 120 ± 5 microns.The zeolite filling dimethyl silicone polymer that makes is all made film and is measured its separating property with performance evaluating apparatus, and feed liquid is that the DMC mass fraction is 30% for the MeOH/DMC azeotropic liquid.Separating property under the different temperatures sees Table 4:
Dimethyl silicone polymer under the table 3 different operating temperature is all made membrane separating property
| Operating temperature (℃) | DMC wt.% is surveyed in infiltration | Separation factor alpha | Permeation flux J (kg/m 2·h) |
| 40 | 59.7 | 3.46 | 1.41 |
| 45 | 58.2 | 3.25 | 1.49 |
| 50 | 57.3 | 3.13 | 1.56 |
| 55 | 55.6 | 2.92 | 1.67 |
| 60 | 54.4 | 2.78 | 1.82 |
Zeolite under the table 4 different operating temperature is filled dimethyl silicone polymer and is all made membrane separating property
| Operating temperature (℃) | DMC wt.% is surveyed in infiltration | Separation factor alpha | Permeation flux J (kg/m 2·h) |
| 40 | 63.7 | 4.09 | 1.05 |
| 45 | 62.5 | 3.89 | 1.23 |
| 50 | 60.7 | 3.60 | 1.37 |
| 55 | 59.4 | 3.41 | 1.46 |
| 60 | 57.6 | 3.17 | 1.55 |
Claims (3)
1. the preparation method of the infiltrating and vaporizing membrane of a preferential saturating dimethyl carbonate, it is characterized in that, comprise the steps: room temperature vulcanized silicone rubber, solvent and zeolite after stirring and ultrasonic mixing, in above-mentioned mixed liquor, add crosslinking agent and catalyst, and stir, be mixed into preparation liquid, wherein the mass ratio of sulphurated siliastic and solvent, crosslinking agent, catalyst is 1: 2: 0.3: 0.06; The zeolite loading is 10～40wt% of total amount; On substrate, scrape to make and all make film, at room temperature place 24h, solvent is fully volatilized, the sulfuration film forming, thickness is 120 ± 5 microns; Wherein said crosslinking agent is ethyl orthosilicate, MTES or vinyltrimethoxy silane; Described catalyst is a dibutyl tin laurate.
2. preparation method according to claim 1 is characterized in that described sulphurated siliastic is 107 glue, 108 glue or 201 glue.
3. preparation method according to claim 1 is characterized in that described solvent is n-hexane, normal heptane or n-decane.
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| CN2007101767542A CN101229491B (en) | 2007-11-02 | 2007-11-02 | Method of preparing pervaporation film preferentially penetrating methyl carbonate |
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|---|---|---|---|
| CN2007101767542A CN101229491B (en) | 2007-11-02 | 2007-11-02 | Method of preparing pervaporation film preferentially penetrating methyl carbonate |
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| CN101229491B true CN101229491B (en) | 2010-06-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012076519A1 (en) * | 2010-12-08 | 2012-06-14 | Shell Internationale Research Maatschappij B.V. | Process for purifying dialkyl carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8323747B2 (en) * | 2010-06-25 | 2012-12-04 | Uop Llc | Zeolite containing wash coats for adsorber heat exchangers and temperature controlled adsorbers |
| CN102350233A (en) * | 2011-07-18 | 2012-02-15 | 清华大学 | Preparation method of pervaporation film with preferential penetration of dimethyl carbonate |
| CN102294182B (en) * | 2011-07-18 | 2014-01-15 | 清华大学 | Preparation method of hydrophobic nano mesoporous molecular sieve filling PDMC composite film |
| CN102489189A (en) * | 2011-12-06 | 2012-06-13 | 厦门大学 | Full-silicon zeolite molecular sieve filled silicon rubber composite membrane and preparation method thereof |
| CN107029557B (en) * | 2016-11-30 | 2020-02-07 | 广东电网有限责任公司电力科学研究院 | Preparation method of silicone rubber pervaporation membrane |
| CN111266020B (en) * | 2020-01-19 | 2022-03-01 | 武汉工程大学 | Montmorillonite separation membrane, preparation method and application thereof, and inductance component |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012076519A1 (en) * | 2010-12-08 | 2012-06-14 | Shell Internationale Research Maatschappij B.V. | Process for purifying dialkyl carbonate |
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