CN105617877A - Polyvinyl alcohol composite film as well as preparation method for composite film and application of composite film to pervaporation - Google Patents
Polyvinyl alcohol composite film as well as preparation method for composite film and application of composite film to pervaporation Download PDFInfo
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- CN105617877A CN105617877A CN201510971016.1A CN201510971016A CN105617877A CN 105617877 A CN105617877 A CN 105617877A CN 201510971016 A CN201510971016 A CN 201510971016A CN 105617877 A CN105617877 A CN 105617877A
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- polyvinyl alcohol
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- compound film
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- alcohol compound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- 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
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- 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
- B01D67/0013—Casting processes
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- 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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a polyvinyl alcohol composite film as well as a preparation method for the composite film and an application of the composite film to the pervaporation. The polyvinyl alcohol composite film is prepared by mixing polyvinyl alcohol and tetraethoxysilane as raw materials according to a mass ratio of (4-50) to (0.05-1). The preparation method comprises the following steps: (1) adding polyvinyl alcohol (PVA) into de-ionized water and stirring in a water bath until PVA is completely dissolved; (2) after cooling, adding hydrochloric acid and tetraethoxysilane (TEOS), stirring at the room temperature, standing, and performing defoaming to obtain a casting film liquid; and (3) pouring the casting film liquid on a polyfluortetraethylene plate, scraping flatly by using a scraper, and performing aeration-drying at 40-60 DEG C for 12-24 hours to obtain the polyvinyl alcohol composite film.
Description
Technical field
The present invention relates to technical field of membrane separation, be specifically related to a kind of polyvinyl alcohol compound film and preparation method thereof and its application in pervaporation.
Background technology
Esterification is an important reaction in organic synthesis, owing to course of reaction is reversible, causes that reaction transformation efficiency is relatively low, how to improve its conversion ratio and become an important research topic. By to the design of reactor, adopt effective catalyst, constantly remove reaction generate water etc. can improve reaction conversion ratio. Relative to improvement and the replacing effective catalyst of reactor, by suitable method, the water generated in course of reaction being removed the advantage of lower cost that this method needs to increase, suitably reduction reaction temperature can reduce energy consumption of reaction simultaneously. The current conventional method of the water produced in reaction of removing has rectification method and molecular sieve drying method etc., but these methods exist the shortcomings such as process complexity, energy consumption height and product yield are low. A kind of novel membrane separation technique is suggested pervaporation, and it has the features such as separation is high, simple to operate, energy consumption is little and easy to implement, is gradually applied in petro chemical industry, pharmaceuticals industry and food industry etc.
Pervaporation (Pervaporation, be called for short PV) is to form vacuum at the infiltration avris of film, with the chemical potential difference of the both sides, front and back of film for motive force along with phase transformation, by film select absorption and in film infiltration rate different and be easily separated. Owing to separation process having only to a kind of component of vaporizing, it is necessary to the energy of consumption is substantially reduced, such that it is able to reduce cost, and does not introduce other components in separation process, and therefore this technology itself has the advantage polluting few even no pollution. Compared with the separation methods such as traditional distillation, extraction, pervaporation has the technical characterstics such as separation is high, simple to operate, energy consumption is little and easy to implement, particularly in nearly boiling point, the azeotropic system more advantage of separation, so at organics dehydration, removing in Organic substance and Organic substance and separating organic matters from water and have a wide range of applications. The key factor affecting pervaporation effect includes physicochemical property and the operating procedure such as temperature, pressure of osmotic evaporation film. For pervaporation, the character of film is to affect the central factor of separation efficiency, selectivity and permeation flux, selects suitable membrane material and is modified as required, is the technological difficulties of pervaporation technology.
Polyvinyl alcohol (be called for short PVA), for white plates, cotton-shaped or Powdered organic compound, is characterized as being that compactness is good, degree of crystallinity is high, and filming performance is excellent, and the film made is pliable and tough, oil resistant, gas barrier are good. The more important thing is, polyvinyl alcohol film is high to water and organic separation selectivity, and this is conducive to it to separate application at the pervaporation of esterification reaction product water. And itself is harmless to human non-toxic, environment is also had good affinity, can be degraded by microorganisms in soil degradable, generate carbon dioxide and water, free from environmental pollution, pervaporation has very important application. But, the problems such as pure polyvinyl alcohol film exists bad mechanical strength, high swelling property, height is adhesive, permeation flux is high. Therefore, polyvinyl alcohol film being carried out suitable modifiying, being conducive to improving permeability and separation effect, thus improving esterification conversion ratio.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, the invention provides a kind of polyvinyl alcohol compound film for the separation of esterification reaction product pervaporation and preparation method thereof and the application in pervaporation, improve the problems such as the bad mechanical strength of polyvinyl alcohol film existence, high swelling property, improve the compactness of composite membrane of polyvinyl alcohol, reduce the permeation flux etc. of film, thus improving the conversion ratio of esterification.
The purpose of the present invention is achieved through the following technical solutions.
The preparation method of a kind of polyvinyl alcohol compound film, is (4��50) according to polyvinyl alcohol and tetraethyl orthosilicate mass ratio: (0.05��1) carries out dispensing, and preparation method comprises the following steps:
(1) polyvinyl alcohol (PVA) is added in deionized water, being placed in stirred in water bath until being completely dissolved, obtaining polyvinyl alcohol water solution;
(2) add hydrochloric acid and tetraethyl orthosilicate (TEOS) after cooling, stir under room temperature, standing and defoaming, obtain casting solution;
(3) being poured on polyfluortetraethylene plate by casting solution, by doctor blade, at 30-80 DEG C, aeration-drying 6-24h, obtains polyvinyl alcohol compound film.
Further, following steps are specifically included:
(1) after deionized water being preheated to 90-100 DEG C, add polyvinyl alcohol, maintaining 90-100 DEG C of stirring until being completely dissolved, obtaining polyvinyl alcohol water solution;
(2) add hydrochloric acid and tetraethyl orthosilicate after cooling, stir 4-12h, standing and defoaming under room temperature, obtain casting solution;
(3) being poured on polyfluortetraethylene plate by casting solution, by doctor blade, at 40-80 DEG C, aeration-drying 6-24h, obtains polyvinyl alcohol compound film.
Further, step (1) described polyvinyl alcohol is the degree of polymerization is 1700��2400, and alcoholysis degree is the polyvinyl alcohol of 78%��98%.
Further, in step (1) described polyvinyl alcohol water solution, the mass fraction of polyvinyl alcohol is 1��10%.
Further, step (2) described concentration of hydrochloric acid is 0.1��2mol/mL.
A kind of polyvinyl alcohol compound film prepared by above-mentioned preparation method.
Above-mentioned a kind of polyvinyl alcohol compound film is applied in esterification pervaporation and dewaters in system.
Compared with prior art, the invention have the advantages that: film preparation process is simple, and the prices of raw materials are cheap, and masking cost is low, applied to butyl acetate esterification, can improve conversion ratio and butyl acetate productivity.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Weighing the addition 5.0g degree of polymerization after 45g deionized water is warming up to 90 DEG C is 1700, alcoholysis degree is the polyvinyl alcohol (PVA) of 78%, stirring to polyvinyl alcohol is completely dissolved, prepared mass fraction is the polyvinyl alcohol water solution of 10%, after being cooled to room temperature, after adding the hydrochloric acid solution that 5mL concentration is 0.1mol/mL, add 0.25g tetraethyl orthosilicate (TEOS), 0.5h deaeration is stood after stirring 4h under room temperature, obtain casting solution, casting solution is poured on polyfluortetraethylene plate, by doctor blade, after 40 DEG C of aeration-drying 24h, obtain polyvinyl alcohol compound film (film 1), this film is used in butyl acetate reaction, assaying reaction conversion ratio is 79.53%.
Embodiment 2
Weighing the addition 0.5g degree of polymerization after 49.5g deionized water is warming up to 90 DEG C is 2400, alcoholysis degree is the polyvinyl alcohol (PVA) of 88%, stirring to polyvinyl alcohol is completely dissolved, prepared mass fraction is the polyvinyl alcohol water solution of 1%, after being cooled to room temperature, after adding the hydrochloric acid solution that 0.25ml concentration is 2mol/mL, add 0.05g tetraethyl orthosilicate (TEOS), 0.5h deaeration is stood after stirring 8h under room temperature, obtain casting solution, casting solution is poured on polyfluortetraethylene plate, by doctor blade, after 80 DEG C of aeration-drying 6h, obtain polyvinyl alcohol compound film (film 2), this film is used in butyl acetate reaction, assaying reaction conversion ratio is 75.56%.
Embodiment 3
Weighing the addition 1.0g degree of polymerization after 49g deionized water is warming up to 90 DEG C is 1700, alcoholysis degree is the polyvinyl alcohol (PVA) of 98%, stirring to polyvinyl alcohol is completely dissolved, prepared mass fraction is the polyvinyl alcohol water solution of 2%, after being cooled to room temperature, after adding the hydrochloric acid solution that 0.5ml concentration is 1mol/mL, add 0.2g tetraethyl orthosilicate (TEOS), 0.5h deaeration is stood after stirring 12h under room temperature, obtain casting solution, casting solution is poured on polyfluortetraethylene plate, by doctor blade, after 60 DEG C of aeration-drying 18h, obtain polyvinyl alcohol compound film (film 3), this film is used in butyl acetate reaction, assaying reaction conversion ratio is 78.43%.
Embodiment 4
Weighing the addition 2.5g degree of polymerization after 47.5g deionized water is warming up to 90 DEG C is 2000, alcoholysis degree is the polyvinyl alcohol (PVA) of 88%, stirring to polyvinyl alcohol is completely dissolved, prepared mass fraction is the polyvinyl alcohol water solution of 5%, after being cooled to room temperature, after adding the hydrochloric acid solution that 0.5ml concentration is 1mol/mL, add 0.75g tetraethyl orthosilicate (TEOS), 0.5h deaeration is stood after stirring 8h under room temperature, obtain casting solution, casting solution is poured on polyfluortetraethylene plate, by doctor blade, after 60 DEG C of aeration-drying 18h, obtain polyvinyl alcohol compound film (film 4), this film is used in butyl acetate reaction, assaying reaction conversion ratio is 77.92%.
Comparative example 1
Weighing the addition 1.0g degree of polymerization after 49g deionized water is warming up to 90 DEG C is 1700, alcoholysis degree is the polyvinyl alcohol (PVA) of 88%, stirring to polyvinyl alcohol is completely dissolved, prepared mass fraction is the polyvinyl alcohol water solution of 2%, after being cooled to room temperature, obtain casting solution, casting solution is poured on polyfluortetraethylene plate, by doctor blade, after 60 DEG C of aeration-drying 18h, obtaining polyvinyl alcohol compound film (film 5), be used for by this film in butyl acetate reaction, assaying reaction conversion ratio is 67.09%.
Table 1 show the film 1 obtained by above-described embodiment, film 2, film 3, and film 4 is for butyl acetate esterification (reaction temperature is 110 DEG C, and the response time is 2h) conversion ratio and comparative example reaction result.
Table 1
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted by the embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. the preparation method of a polyvinyl alcohol compound film, it is characterised in that be (4 ~ 50) according to polyvinyl alcohol and tetraethyl orthosilicate mass ratio: (0.05 ~ 1) carries out dispensing, and preparation method comprises the following steps:
(1) polyvinyl alcohol is added in deionized water, being placed in stirred in water bath until being completely dissolved, obtaining polyvinyl alcohol water solution;
(2) add hydrochloric acid and tetraethyl orthosilicate after cooling, stir under room temperature, standing and defoaming, obtain casting solution;
(3) being poured on polyfluortetraethylene plate by casting solution, by doctor blade, at 30-80 DEG C, aeration-drying 6-24h, obtains polyvinyl alcohol compound film.
2. the preparation method of a kind of polyvinyl alcohol compound film according to claim 1, it is characterised in that specifically include following steps:
(1) after deionized water being preheated to 90-100 DEG C, add polyvinyl alcohol, maintaining 90-100 DEG C of stirring until being completely dissolved, obtaining polyvinyl alcohol water solution;
(2) add hydrochloric acid and tetraethyl orthosilicate after cooling, stir 4-12h, standing and defoaming under room temperature, obtain casting solution;
(3) being poured on polyfluortetraethylene plate by casting solution, by doctor blade, at 30-80 DEG C, aeration-drying 6-24h, obtains polyvinyl alcohol compound film.
3. the preparation method of a kind of polyvinyl alcohol compound film according to any one of claim 1-2, it is characterised in that step (1) described polyvinyl alcohol is the degree of polymerization is 1700 ~ 2400, and alcoholysis degree is the polyvinyl alcohol of 78% ~ 98%.
4. the preparation method of a kind of polyvinyl alcohol compound film according to any one of claim 1-2, it is characterised in that in step (1) described polyvinyl alcohol water solution, the mass fraction of polyvinyl alcohol is 1 ~ 10%.
5. the preparation method of a kind of polyvinyl alcohol compound film according to any one of claim 1-2, it is characterised in that step (2) described concentration of hydrochloric acid is 0.1 ~ 2mol/mL.
6. a kind of polyvinyl alcohol compound film that the preparation method described in claim 1 prepares.
7. a kind of polyvinyl alcohol compound film described in claim 6 is applied in esterification pervaporation and dewaters in system.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971016.1A CN105617877A (en) | 2015-12-20 | 2015-12-20 | Polyvinyl alcohol composite film as well as preparation method for composite film and application of composite film to pervaporation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510971016.1A CN105617877A (en) | 2015-12-20 | 2015-12-20 | Polyvinyl alcohol composite film as well as preparation method for composite film and application of composite film to pervaporation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011180A (en) * | 2022-06-24 | 2022-09-06 | 浙江奥首材料科技有限公司 | Double-component base liquid, cutting protection liquid, preparation method, application and cutting method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0436128A1 (en) * | 1989-12-01 | 1991-07-10 | Deutsche Carbone AG | Composite membranes for separating water from organic compounds containing fluids |
| CN1907550A (en) * | 2006-07-24 | 2007-02-07 | 浙江大学 | Preparation method for hollow fiber osmosis vaporation permeable complex film |
| CN102029116A (en) * | 2010-10-27 | 2011-04-27 | 合肥学院 | Preparation method of polyvinyl alcohol pervaporation hybrid membrane |
-
2015
- 2015-12-20 CN CN201510971016.1A patent/CN105617877A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0436128A1 (en) * | 1989-12-01 | 1991-07-10 | Deutsche Carbone AG | Composite membranes for separating water from organic compounds containing fluids |
| CN1907550A (en) * | 2006-07-24 | 2007-02-07 | 浙江大学 | Preparation method for hollow fiber osmosis vaporation permeable complex film |
| CN102029116A (en) * | 2010-10-27 | 2011-04-27 | 合肥学院 | Preparation method of polyvinyl alcohol pervaporation hybrid membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011180A (en) * | 2022-06-24 | 2022-09-06 | 浙江奥首材料科技有限公司 | Double-component base liquid, cutting protection liquid, preparation method, application and cutting method |
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Application publication date: 20160601 |