CN101219347A - Pervaporation membrane for esterification reaction and method for producing the same - Google Patents
Pervaporation membrane for esterification reaction and method for producing the same Download PDFInfo
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- CN101219347A CN101219347A CNA2007100603634A CN200710060363A CN101219347A CN 101219347 A CN101219347 A CN 101219347A CN A2007100603634 A CNA2007100603634 A CN A2007100603634A CN 200710060363 A CN200710060363 A CN 200710060363A CN 101219347 A CN101219347 A CN 101219347A
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Abstract
The invention relates to a permeable pervaporation membrane used in esterification and a preparation method thereof. The permeable pervaporation membrane employs chitosan and ethyl orthosilicate as raw materials which are matched according to the weight ratio between the chitosan and the ethyl orthosilicate is 10: 0.5-50:1. The preparation method is that the chitosan (CS) is dissolved into acetic acid hydrosolution and then is stirred in water bath of 80 DEG C, thus obtaining chitosan solution; the chitosan solution is filtered before the ethyl orthosilicate is added for stirring for 2 hours under room temperature, thus obtaining casting solution through stewing and deaerating; the casting film solution is ventilated and dried for 48 hours under 20-30 DEG C and is heat treated for 2 hours under 120 DEG C, thus obtaining CS-TEOS hybrid membranes. The invention has simple preparation, abundant raw materials and low cost; the CS-TEOS hybrid membranes being prepared can be used in the esterification for permeating and evaporating dehydration in coupling process to improve the yield of ethyl lactate, water permeable flux reaches 97.5g m<-2>h<-1> and the yield of the ethyl lactate is improved from 66.4 percent to 80.0 percent.
Description
Technical field
The present invention relates to the pervaporation membrane preparation technology, particularly a kind of osmotic evaporation film that is used for esterification and preparation method thereof is hybrid organic-inorganic film that is used to dewater in the esterification reaction-infiltration evaporation coupling technique and preparation method thereof specifically.
Background technology
Ethyl lactate is a kind of important fine chemical material, and food industry is widely used in spices, spices synergist and Wine additive, can be used to allocate flavoring essence, wine with essence and foodstuff flavouring fumet, also can be used for modulating soft drink and inebriant.Because ethyl lactate contains asymmetric carbon atom, therefore have two kinds of optical isomers, it also is a kind of optically active essential industry solvent that has, can be used as the solvent of nitrocellulose, acetate fiber, alkyd resins, shell pine ester, Manila copal, rosin, shellac, vinyl, paint etc., still is the senior solvent of olivet class simultaneously.Other industry also are used to do plasticizer, can be used for synthetic having optically active carboxylate in asymmetric syntheses, are used as lubricant, medicine pindolol intermediate of slugging or the like in the pharmacy.Therefore in industries such as food, wine brewing, chemical industry, medicine extensive use is arranged.Traditional ethyl lactate production is to be raw material with lactic acid and ethanol, as catalyst, comes direct esterification Synthesis of ethyl lactate with benzene, toluene, the water that removes in the dereaction as the band aqua with the concentrated sulfuric acid.Even deviating from reaction product water for esterification will promote esterification greatly and carry out, the technology of exploitation has rectification method, molecular sieve drying method etc. to remove the direct Synthesis of ethyl lactate of esterification moisture at present, these methods also exist the reaction temperature height to cause that energy consumption is big, material loss causes shortcomings such as expense height greatly, thereby be necessary the ethyl lactate synthesis technique of development of new fully, existing higher esterification conversion ratio and ethyl lactate productive rate can be realized low reaction temperatures, low energy consumption and low-cost production again.
Pervaporation (pervaporation is called for short PV or PVAP) also claims infiltration evaporation, is one of the focus in present film Separation Research field.As the new separation technology of liquid mixture, efficient, energy-conservation, characteristics such as technology simple, environmental friendliness that pervaporation has are described as " green technology ", infiltration evaporation is used for dehydration esterification reaction is of practical significance very much.Undergo phase transition and separate owing to have only in this coupling technique water to see through film, therefore have energy-saving effect preferably.People such as Waldburge think that with respect to conventional esterification technique the esterification membrane reactor can reduce by 75% energy consumption, reduce by 50% running cost.The selection of pervaporation membrane material and the preparation of film are the keys of coupling technique.Can make the good pervaporation dewatering membrane that is used for pervaporation-esterification coupling technique by modification to existing membrane material.
The existing osmotic evaporation film that is used for esterification reaction-infiltration evaporation coupling technique can be divided into the inorganic material film based on zeolite, based on the hydrophilic film material of polyvinyl alcohol, shitosan etc., adopt CS-TEOS hybrid organic-inorganic film material to be used for the esterification reaction-infiltration dehydration by evaporation and do not see bibliographical information.
Summary of the invention
The object of the present invention is to provide a kind of osmotic evaporation film that is used for esterification and preparation method thereof, to be used for the esterification reaction-infiltration dehydration by evaporation with the CS-TEOS hybridized film of this method preparation, the promotion performance that has higher dewatering and ethyl lactate is generated.
The osmotic evaporation film that is used for esterification provided by the invention is to be raw material with shitosan and ethyl orthosilicate, comprises the steps: according to shitosan and ethyl orthosilicate mass ratio 10～50: 0.5～1 its preparation method of preparing burden
1) with shitosan (CS) dissolving acetic acid aqueous solution first, stirred in water bath to shitosan dissolves fully, makes chitosan aqueous solution;
2) filter the back and add ethyl orthosilicate (TEOS), stir under the room temperature, standing and defoaming obtains casting solution;
3) casting solution is poured on the poly (methyl methacrylate) plate, uses the scraper knifing, aeration-drying 120 ℃ of following heat treatments, gets the CS-TEOS hybridized film.
The preparation method who is used for the osmotic evaporation film of esterification provided by the invention comprises the steps:
1) with in shitosan (CS) the dissolving acetic acid aqueous solution, dissolves fully, make chitosan aqueous solution in 80 ℃ of stirred in water bath to shitosans;
2) filter the back and add ethyl orthosilicate (TEOS), stir standing and defoaming after 2 hours under the room temperature, obtain casting solution;
3) casting solution is poured on the poly (methyl methacrylate) plate, uses the scraper knifing, 20～30 ℃ of following aeration-drying 48 hours, 120 ℃ of following heat treatments 2 hours, the CS-TEOS hybridized film.
The described acetic acid aqueous solution of step 1) is 2% acetic acid aqueous solution.
The described chitosan aqueous solution of step 1) is 2% chitosan aqueous solution.
The above-mentioned CS-TEOS hybridized film that makes is used for the dehydration of esterification reaction-infiltration evaporation coupling process improves the ethyl lactate productive rate, the water permeation flux reaches 97.5gm
-2h
-1, the ethyl lactate productive rate brings up to 80.0% by 66.4%.
The invention has the advantages that: the film preparation process is simple, and controllability is strong.Raw material sources are abundant, and are cheap, and system film cost is low.The CS-TEOS hybridized film is used for the dehydration of esterification reaction-infiltration evaporation coupling process and improves the ethyl lactate productive rate, and the water permeation flux reaches 97.5gm
-2h
-1, the ethyl lactate productive rate can bring up to 80.0% by 66.4%.
The specific embodiment
Embodiment 1
3.0g shitosan (CS) is joined in the acetic acid aqueous solution of 147g 2wt%, being stirred to shitosan with the rotating speed of 500r/min in 80 ℃ of water-baths dissolves fully, make 2wt% concentration and get chitosan aqueous solution, filter the back and add 0.18g ethyl orthosilicate (TEOS), stir after 2 hours under the room temperature and leave standstill the 20min deaeration, obtain casting solution, casting solution is poured on the clean poly (methyl methacrylate) plate, use the scraper knifing, behind 25 ℃ of following aeration-drying 48h, in electrically heated drying cabinet,, make CS-TEOS hybridized film (film 1), film average thickness 50 μ m in 120 ℃ of following heat treatment 2h.This film is used for the esterification reaction-infiltration evaporation process, obtains water permeation flux 97.5gm
-2h
-1, ethyl lactate productive rate 80.0wt%.
Embodiment 2
3.0g shitosan (CS) is joined in the acetic acid aqueous solution of 147g 2wt%, being stirred to shitosan with the rotating speed of 500r/min in 80 ℃ of water-baths dissolves fully, make 2wt% concentration and get chitosan aqueous solution, filter the back and add 0.3g ethyl orthosilicate (TEOS), stir after 2 hours under the room temperature and leave standstill the 20min deaeration, obtain casting solution, casting solution is poured on the clean poly (methyl methacrylate) plate, use the scraper knifing, behind 25 ℃ of following aeration-drying 48h, in electrically heated drying cabinet,, make CS-TEOS hybridized film (film 2), film average thickness 50 μ m in 120 ℃ of following heat treatment 2h.This film is used for the esterification reaction-infiltration evaporation process, obtains water permeation flux 66.4gm
-2h
-1, ethyl lactate productive rate 74.9wt%.
Embodiment 3
3.0g shitosan (CS) is joined in the acetic acid aqueous solution of 147g 2wt%, being stirred to shitosan with the rotating speed of 500r/min in 80 ℃ of water-baths dissolves fully, make 2wt% concentration and get chitosan aqueous solution, filter the back and add 0.6g ethyl orthosilicate (TEOS), stir after 2 hours under the room temperature and leave standstill the 20min deaeration, obtain casting solution, casting solution is poured on the clean poly (methyl methacrylate) plate, use the scraper knifing, behind 25 ℃ of following aeration-drying 48h, in electrically heated drying cabinet,, make CS-TEOS hybridized film (film 3), film average thickness 50 μ m in 120 ℃ of following heat treatment 2h.This film is used for the esterification reaction-infiltration evaporation process, obtains water permeation flux 114.8gm
-2h
-1, ethyl lactate productive rate 68.8wt%.
Embodiment 4
3.0g shitosan (CS) is joined in the acetic acid aqueous solution of 147g 2wt%, being stirred to shitosan with the rotating speed of 500r/min in 80 ℃ of water-baths dissolves fully, make 2wt% concentration and get chitosan aqueous solution, filter the back and add 1.35g ethyl orthosilicate (TEOS), stir after 2 hours under the room temperature and leave standstill the 20min deaeration, obtain casting solution, casting solution is poured on the clean poly (methyl methacrylate) plate, use the scraper knifing, behind 25 ℃ of following aeration-drying 48h, in electrically heated drying cabinet,, make CS-TEOS hybridized film (film 4), film average thickness 50 μ m in 120 ℃ of following heat treatment 2h.This film is used for the esterification reaction-infiltration evaporation process, obtains water permeation flux 108.3gm
-2h
-1, ethyl lactate productive rate 74.0wt%.
Comparative Examples 1
To be heated to 80 ℃ in the 120g ethanol adding reaction unit, take by weighing and join in the reaction unit with 1.56g catalyst A mberlyst 15 78g lactic acid is heated to 80 ℃ in water-bath after, t=0 picks up counting, form every 1h analytical reactions thing, when reaction proceeded to 9h, the ethyl lactate productive rate was 66.4wt%.
Table 1 is depicted as the prepared film 1 of embodiment, and film 2, film 3, film 4 are used for behind lactic acid/ethyl esterification reaction-pervaporation and independent lactic acid/ethyl esterification reaction result.
Table 1
| Film number | TEOS/CS mass percent (%) | Reaction temperature (℃) | Reaction time (h) | Initial molar ratio of alcohol to acid | Water permeation flux (gm -2h -1) | Ethyl lactate productive rate wt% |
| Film 1 film 2 films 3 films 4 films 5 | 6 10 20 45 - | 80 80 80 80 80 | 9 9 9 9 9 | 3 3 3 3 3 | 97.5 66.4 114.8 108.3 - | 80.0 74.9 68.8 74.0 66.4 |
Claims (5)
1. osmotic evaporation film that is used for esterification is characterized in that it is is raw material with shitosan and ethyl orthosilicate, prepares burden according to shitosan and ethyl orthosilicate mass ratio 10～50: 0.5～1, and its preparation method may further comprise the steps:
1) shitosan is dissolved in the acetic acid aqueous solution, stirred in water bath to shitosan dissolves fully, makes chitosan aqueous solution;
2) filter the back and add ethyl orthosilicate, stir under the room temperature, standing and defoaming obtains casting solution;
3) casting solution is poured on the poly (methyl methacrylate) plate, uses the scraper knifing, aeration-drying 120 ℃ of following heat treatments, gets the CS-TEOS hybridized film.
2. the described preparation method who is used for the osmotic evaporation film of esterification of claim 1 is characterized in that it is to comprise the steps:
1) with in shitosan (CS) the dissolving acetic acid aqueous solution, dissolves fully, make chitosan aqueous solution in 80 ℃ of stirred in water bath to shitosans;
2) filter the back and add ethyl orthosilicate (TEOS), stir standing and defoaming after 2 hours under the room temperature, obtain casting solution;
3) casting solution is poured on the poly (methyl methacrylate) plate, uses the scraper knifing, 20～30 ℃ of following aeration-drying 48 hours, 120 ℃ of following heat treatments 2 hours, the CS-TEOS hybridized film.
3. preparation method according to claim 2 is characterized in that the described acetic acid aqueous solution of step 1) is 2% acetic acid aqueous solution.
4. preparation method according to claim 2 is characterized in that the described chitosan aqueous solution of step 1) is 2% chitosan aqueous solution.
5. the described osmotic evaporation film that is used for esterification of claim 1 is used for the synthetic of ethyl lactate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100603634A CN101219347A (en) | 2007-12-19 | 2007-12-19 | Pervaporation membrane for esterification reaction and method for producing the same |
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|---|---|---|---|
| CNA2007100603634A CN101219347A (en) | 2007-12-19 | 2007-12-19 | Pervaporation membrane for esterification reaction and method for producing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786706A (en) * | 2012-08-10 | 2012-11-21 | 李大纲 | Preparation method for biomass nano composite film with chitin as basic material |
| CN102085459B (en) * | 2009-12-03 | 2013-02-13 | 中国石油天然气股份有限公司 | Method for preparing anti-polluting oil-water separation ultra-filtration membrane |
| CN109603579A (en) * | 2018-12-03 | 2019-04-12 | 宁波大学 | A kind of preparation method and applications of chitin-tetraethyl orthosilicate composite membrane |
-
2007
- 2007-12-19 CN CNA2007100603634A patent/CN101219347A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102085459B (en) * | 2009-12-03 | 2013-02-13 | 中国石油天然气股份有限公司 | Method for preparing anti-polluting oil-water separation ultra-filtration membrane |
| CN102786706A (en) * | 2012-08-10 | 2012-11-21 | 李大纲 | Preparation method for biomass nano composite film with chitin as basic material |
| CN102786706B (en) * | 2012-08-10 | 2013-12-18 | 李大纲 | Preparation method for biomass nano composite film with chitin as basic material |
| CN109603579A (en) * | 2018-12-03 | 2019-04-12 | 宁波大学 | A kind of preparation method and applications of chitin-tetraethyl orthosilicate composite membrane |
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