CN103007783A - Preparation method of cellulose ether-ethyl orthosilicate pervaporation hybrid membrane - Google Patents
Preparation method of cellulose ether-ethyl orthosilicate pervaporation hybrid membrane Download PDFInfo
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Abstract
The invention discloses a pervaporation hybrid membrane for separating a methanol water solution and a preparation method thereof. The hybrid membrane is prepared from raw materials cellulose ether and ethyl orthosilicate. The preparation method comprises the following steps: blending and hybridizing the cellulose ether and ethyl orthosilicate to obtain a membrane casting solution; forming the membrane by a solution casting method; lightly crosslinking the membrane with a chemical crosslinking agent; and preparing the cellulose ether pervaporation hybrid membrane for separating the methanol water solution. The organic-inorganic hybrid membrane prepared by the method is a high-hydrophilicity pervaporation membrane, is suitable for dehydrating organic solvents, especially has favorable separation effect on the methanol water solution which can not be effectively separated by other membranes, and also has favorable separation effect on water solutions of ethanol, isopropanol and the like.
Description
Technical field
The invention belongs to the infiltrating and vaporizing membrane technical field, be specifically related to a kind of cellulose ether for separating of methanol aqueous solution-ethyl orthosilicate infiltration evaporation hybridized film and preparation method thereof.
Background technology
Infiltration evaporation (Pervaporation is called for short PV) is a kind of film separation process for the liquid mixture separation.It utilizes, and permeable pressure head is driving force between each component, relies on each component to dissolve in film and reach with diffusion rate difference to separate purpose.Compare with separating technologies such as traditional rectifying, absorption, extractions, it has the separative efficiency height, equipment is simple, easy and simple to handle, process is pollution-free, low power consumption and other advantages.PV more shows the advantage that it is unique in the separating of the high mixed system of nearly boiling point mixture, azeotropic mixture and temperature sensitivity.Be the technology that is at present development period and period of expansion, be with a wide range of applications in fields such as petrochemical industry, medicine, food, biotechnology, environmental protection.To the nineties, begin to realize industrialization, be called 21 century one of the most promising new and high technology by the brainstrust of international academic community.
Infiltration evaporation can be used for organics dehydration, recovery organic matter, organic matter separation, wherein organics dehydration most study.At present, be tending towards ripe about the infiltration evaporation isolation technics of the alcohol solutions such as ethanol, isopropyl alcohol, butanols, tentatively realized industrialization, but the infiltration evaporation of methanol aqueous solution separates and still be in laboratory stage, relevant research report both domestic and external is few.Reason is to compare with ethanol, isopropyl alcohol equimolecular, and the molecular structure of methyl alcohol, polarity are very similar to water, cause methyl alcohol and the suction-operated of water in diffusion barrier to be competed mutually, thereby makes methyl alcohol and shipwreck to separate.So Methanol-biodiesel ﹠ Its manufacturing enterprise adopts the method separating-purifying methanol aqueous solutions such as ion exchange resin, rectifying usually at present, but its process is complicated, and energy consumption is higher, and the production cost of biodiesel is increased, and advantage is not obvious in market competition; Developing separation of methanol aqueous solution infiltrating and vaporizing membrane can reach in the methanol removal a small amount of water and obtain high-purity methyl alcohol or break fast alcohol-water azeotropic point.Therefore obtaining high score is vital from the application of factor pair methanol crossover vaporization.
At present, the advantages such as organic polymer films has that pliability is good, good penetrability, density are low, low price and good film-forming property, but its anti-solvent, corrosion-resistant and heat resistance is all relatively poor can not provide enough selective and permeation fluxs to some systems.And high, corrosion-resistant, the anti-solvent of inoranic membrane intensity and high temperature resistant, but inorganic material is crisp, is difficult for processing, and film forming is poor, and price is also relatively more expensive at present.In order to concentrate organic film and inoranic membrane advantage separately, people have designed organic-inorganic hybrid membrane.This film has good physical and chemical stability and separating property, and good film-forming property, has become the study hotspot in the fields such as macromolecule and material science, membrane material preparation.According to the interaction type between organic and inorganic component, hybrid inorganic-organic materials can be divided into two large classes: a class be between organic and inorganic component with the hybrid material of weak interaction-secondary bond (Van der Waals force, hydrogen bond or weak electrostatic interaction) combination, form the composite with embedding phase.Another kind of is with the hybrid material of strong interaction-chemical bond (such as covalent bond, ion-covalent bond and coordinate bond) combination between organic and inorganic component.Combine closely by strong chemical bond between organic and inorganic component in this class hybridized film and form the good hybrid material of compatibility, improved the performance of homogenous material.
The rubbery state main chain is soft, with inorganic particulate preferably compatibility is arranged, and this is so that inorganic particulate and Polymers physical efficiency are compatible well, and alternate combination is tight; And the glassy polymers chain is harder, and itself and inorganic particulate compatibility are undesirable, easily is separated around inorganic particulate, forms the non-selectivity hole, the reduction film selectively.Therefore the research before mainly concentrates on rubbery feel polymer, such as dimethyl silicone polymer (PDMS), acrylic nitrile-butadiene-styrene terpolymer (ABS), shitosan (CS), ethylene propylene diene rubber (EPDM) etc.And in glassy polymers, main chain is a kind of rigid chain, and motion only is confined to the vibration of segment, and free volume is little than rubbery feel polymer, and infiltration component is had higher permselective property, but permeation flux is generally lower.In the glassy polymers film, fill inorganic particulate and can improve permeability of the membrane.Also some glassy polymers are studied at present, such as polysulfones (PSF), polyimides (PI), cellulose acetate (CA) and poly-acetimide (PEI) etc.
Chinese patent application 201010523943.4 discloses and has been used for a kind of method that removes the saturating pure hybridized film of infiltration evaporation of waste water methyl alcohol, and this is a kind of preferential alcohol permselective membrane, be applicable to the processing of the low concentration methanol aqueous solution, and separation factor is lower.
Chinese patent application 200710040764.3 has been announced a kind of at the chemical vapour deposition (CVD) of macropore ceramic membrane surface, glycerol polymerization and the hydrophilic osmotic vaporization compound membrane of ring-opening reaction preparation take inorganic ceramic membrane as carrier, has shown very excellent performance in the separation of methanol aqueous solution.But the method preparation process is complicated, and severe reaction conditions is with high costs, and needs the organic solvent that uses toxicity larger in the preparation process.
Chinese patent application 200610052633.2 discloses a kind of preparation method of hollow fiber osmosis vaporation permeable complex, and polyvinyl alcohol and sodium alginate blended cross linking are made hollow fiber composite membrane.The method technique is simple, and is easy to operate, the separating of applicable and multiple alcohol solution.But polyvinyl alcohol-based hollow fiber memberane is in use easily by the organic matter swelling, and strength decreased after use a period of time the fracture of wire problem occurs, and resistance tocrocking is poor, and system is difficult for operation steady in a long-term, and Flat Membrane has greater advantage in this respect.
Chinese patent 201210247999.0 discloses a kind of sodium alginate infiltration evaporation hybridized film for separating of methanol aqueous solution.The hybrid organic-inorganic film that makes is a kind of infiltrating and vaporizing membrane of high-hydrophilic, other films are difficult to realize that the methanol aqueous solution of effective separation has good separating effect, but separation factor is still waiting further raising.
At present, have no the research of cellulose ether hybridized film in the patent.Cellulose ether since its main chain on circulus so that its strand seems rigidity; But because etherification reaction has destroyed hydrogen bond action strong between the cellulosic molecule, greatly reduce cellulosic degree of crystallinity, make it can be water-soluble, dilute alkaline soln and organic solvent, and has thermoplasticity, the hydrophilic polymer that belongs to glassy state, its wide material sources, cheap, have the gel-free characteristic, and not with ionization, compatibility is good, have simultaneously good biological degradability and biological safety, can be used for preparing the various types of films material, the further improvement but the mechanical property of film and solvent resistance await, wherein methylcellulose and hydroxypropyl methylcellulose dispersiveness are better than hydroxyethylcellulose.Because of the particularity of cellulose ether structure, the membrane structure of its preparation is fine and close, and the methanol molecules approaching to molecular structure and water has good interception function, and the film separation factor is higher.But easily by swelling, excessively swelling will cause the free volume between polymer chain to increase to pure cellulose ether at methanol aqueous solution, and the separation selectivity of film reduces, thereby has limited its application in separation.
Ethyl orthosilicate (TEOS) is the liquid that a kind of water white transparency is easy to volatilize, slightly scent of.It is the product of silicon tetrachloride and ethanol synthesis.In the TEOS structure, chemical bond between alkoxyl and the silicon is very insecure, cause the p-OH of ethyl orthosilicate very responsive, TEOS can be used as inorganic precursor and joins in the cellulose ether film, because the hydrolysis-condensation effect of TEOS, formed-silicon-oxygen polymer of O-Si-O-structure, made to have occurred inierpeneirating network structure in the film.Simultaneously also can form hydrogen bond and covalent bond Si-O-C with cellulose ether after the TEOS hydrolysis, hydroxyl is reduced, thereby the degree of crystallinity that reduces the cellulose ether film forms the homogeneous phase hybrid film, has improved the physical and chemical stability of film.In polymer, fill the microstructure that inorganic particulate can fine adjustment film, increase the porosity of film, change the free volume of film, forms suitable pore structure, thereby improve the separating property of film, and the separation factor of film is along with the addition increase of TEOS and increase.But when the further increase of TEOS content, himself polycondensation reaction aggravation does not have enough hydroxyls that polycondensation reaction occurs with it in the cellulose ether simultaneously, causes the film surface particulate inorganic particle to occur, presents slight phenomenon of phase separation, and the separating property of film is reduced.Introduce crosslinking agent and can suppress being separated of hybrid organic-inorganic film, help to form the homogeneous phase hybrid film system.
Crosslinking agent is of a great variety, for-OH commonly used aldehydes, acids, diisocyanates arranged.This class crosslinking agent belongs to chemical crosslinking, can produce cross-linking reaction between the organic and inorganic phase and form covalent bond.Slight crosslinked being conducive to suppresses to be separated, but the crosslinked permeation flux of film that excessively can cause sharply reduces.
Summary of the invention
It is not high to the objective of the invention is to overcome existing methanol aqueous solution infiltrating and vaporizing membrane separation factor, or the shortcoming such as the preparation process of film is complicated, with high costs.Provide a kind of separation to methanol aqueous solution to have high selectivity, organic-inorganic hybridized osmotic vaporization film that has good stability and preparation method thereof.
One aspect of the present invention relates to a kind of infiltration evaporation hybridized film for separating of methanol aqueous solution, it is characterized in that, the raw material of preparation hybridized film comprises cellulose ether and ethyl orthosilicate, and the step of preparation hybridized film comprises: utilize cellulose ether and ethyl orthosilicate to carry out blend hydridization and obtain casting solution; Utilize solution casting method to make cellulose ether infiltration evaporation hybridized film for separating of methanol aqueous solution.
The present invention also relates to the preparation method of the infiltration evaporation hybridized film of the above-mentioned separation of methanol aqueous solution on the other hand, comprise the steps: a) configuration of casting solution: the preparation cellulose ether aqueous solution, ethyl orthosilicate is mixed with water, make its hydrolysis, then slowly join in the cellulose ether solution, and continue to stir formation homogeneous phase transparent colloidal sol; B) film: polyacrylonitrile micropore counterdie is placed mould, with scraping hymenotome casting solution evenly is coated on the counterdie surface, gelation and dry 48h under room temperature, then at 60-70 ℃ of lower vacuum drying 24h, be soaked in the crosslinker solution gained film crosslinked, remove unreacted impurity with the deionized water cyclic washing at last, drying obtains the cellulose ether hybridized film.
In a preferred embodiment of the present invention, it is characterized in that the mass fraction of ethyl orthosilicate (with respect to cellulose ether) is 0-35wt% among the described step a, does not comprise 0, is preferably 10-25wt%; The mass fraction of cellulose ether solution is 2-10%, is preferably 4-6%.
In a preferred embodiment of the present invention, it is characterized in that, also comprise the pH of solution when regulating teos hydrolysis among the described step a, make it between 1-3.Gained colloidal sol is filtered through the 2# sand core funnel, remove insoluble matter, leave standstill, deaeration gets casting solution.
In a preferred embodiment of the present invention, it is characterized in that mould is any in glass mold, the polytetrafluoroethylene (PTFE) mould among the described step b.
In a preferred embodiment of the present invention, it is characterized in that, described crosslinking agent be in vulcabond, glutaraldehyde, phosphoric acid or the citric acid one or more, preferably vulcabond, glutaraldehyde.
The present invention also relates to the preparation-obtained infiltration evaporation hybridized film of above-mentioned preparation method on the other hand for separating of methanol aqueous solution.
The present invention's advantage compared with prior art: 1, the present invention adopts the form of synthetic inierpeneirating network structure to prepare lightly crosslinked cellulose ether hybrid organic-inorganic film, generally speaking, the pattern of film is more even, and network is clear fine and closely woven, and less defective (seeing Fig. 1,2) is arranged.Owing to be inierpeneirating network structure, therefore the film of preparation has good anti-solvent stability, and the swellbility of film is controlled, and film strength has improved, and main is the separation factor that has improved film.The methanol dehydration infiltrating and vaporizing membrane that provides has that separating property is good, film forming is high, structure and steady performance, is particularly useful for sloughing minor amount of water from low discharge, the high concentration methanol aqueous solution, need not follow-up purification step.Simultaneously, the aqueous solution such as ethanol, isopropyl alcohol also there is preferably separating effect.
2, raw material sources of the present invention are extensive, cheap.Manufacture craft is simple, and is easy to operate, is easy to grasp, and efficient is high, the controllability of membrane structure and production good reproducibility.
Description of drawings
Fig. 1 is the surface scan Electronic Speculum figure of hydroxyethylcellulose/ethyl orthosilicate (15wt%) hybridized film of preparing of the present invention.
Fig. 2 is the section surface sweeping Electronic Speculum figure of hydroxyethylcellulose/ethyl orthosilicate (15wt%) hybridized film of preparing of the present invention.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1: take by weighing the 4g hydroxyethylcellulose and be dissolved in the 100g distilled water, 70 ℃ of lower stirrings until dissolve complete, take by weighing 0.2g(5wt%, with respect to HEC) TEOS, soluble in water make its hydrolysis, the mol ratio of water and TEOS is 5:1, between hydrochloric acid conditioning solution pH to 1-3,, to clarification, slowly join in the hydroxy ethyl fiber cellulose solution until solution reaction, and continue to stir formation homogeneous phase transparent colloidal sol.Gained colloidal sol is filtered through the 2# sand core funnel, remove insoluble matter, leave standstill, deaeration gets casting solution.With scraping hymenotome colloidal sol is coated on polyacrylonitrile counterdie surface, gelation and dry 48h under the room temperature are then at 60-70 ℃ of lower vacuum drying 24h, the gained film is soaked in the crosslinker solution crosslinked, crosslinker solution is the acetone-water solution (1:2, v/v) of 180mL, 2.5mL hydrochloric acid, the 2.5mL glutaraldehyde.Remove unreacted impurity with the deionized water cyclic washing at last, drying obtains the hydroxyethylcellulose hybridized film.The film of gained carries out the osmotic, evaporating and dewatering experiment of methanol aqueous solution, feed liquid is the methanol aqueous solution of variable concentrations, place there-necked flask, and by heating water bath, temperature maintains 30 ℃, feed liquid enters in the membrane module through the peristaltic pump coutroi velocity, then refluxes in there-necked flask, and the effective area of film is 12.56cm
2, behind the about 2h of whole system stable operation, the vavuum pump of opening the film downstream vacuumizes, and vacuum maintains 1.5kPa, and penetrant is collected through cold-trap (liquid nitrogen, its fusing point are-196 ℃) cooling, continues 5h.When feed concentration (methyl alcohol wt%) when being respectively 90%, 95%, permeation flux J(g/m
2H) be respectively 313,287, separation factor alpha is respectively 197,504.
Embodiment 2: such as the processing step of example 1, wherein, the addition that only changes TEOS is 0.4g(10wt%, with respect to HEC), make hydroxyethylcellulose hybrid organic-inorganic film of the present invention.When feed concentration (methyl alcohol wt%) when being respectively 90%, 95%, permeation flux J(g/m
2H) be respectively 270,235, separation factor alpha is respectively 352,812.
Embodiment 3: such as the processing step of example 1, wherein, the addition that only changes TEOS is 0.6g(15wt%, with respect to HEC), make hydroxyethylcellulose hybrid organic-inorganic film of the present invention.When feed concentration (methyl alcohol wt%) when being respectively 90%, 95%, permeation flux J(g/m
2H) be respectively 193,157, separation factor alpha is respectively 699,1319.
Embodiment 4: such as the processing step of example 1, wherein, the addition that only changes TEOS is 1.0g(25wt%, with respect to HEC), make hydroxyethylcellulose hybrid organic-inorganic film of the present invention.When feed concentration (methyl alcohol wt%) when being respectively 90%, 95%, permeation flux J(g/m
2H) be respectively 226,182, separation factor alpha is respectively 535,1027.
Embodiment 5: such as the processing step of example 1, wherein, the addition that only changes TEOS is 1.4g(35wt%, with respect to HEC), make hydroxyethylcellulose hybrid organic-inorganic film of the present invention.When feed concentration (methyl alcohol wt%) when being respectively 90%, 95%, permeation flux J(g/m
2H) be respectively 277,253, separation factor alpha is respectively 387,758.
When being understood that; specific embodiments of the invention only are the purposes of property explanation presented for purpose of illustration; it limits protection scope of the present invention never in any form; those skilled in the art can be improved or conversion according to the above description, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (8)
1. infiltration evaporation hybridized film for separating of methanol aqueous solution, it is characterized in that, the raw material of preparation hybridized film comprises cellulose ether and ethyl orthosilicate, and the step of preparation hybridized film comprises: utilize cellulose ether and ethyl orthosilicate to carry out blend hydridization and obtain casting solution; Utilize solution casting method to make cellulose ether infiltration evaporation hybridized film for separating of methanol aqueous solution.
2. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 1 is characterized in that, comprises the steps:
A) configuration of casting solution: the preparation cellulose ether aqueous solution, ethyl orthosilicate is mixed with water, make its hydrolysis, then slowly join in the cellulose ether solution, and continue to stir formation homogeneous phase transparent colloidal sol;
B) film: polyacrylonitrile micropore counterdie is placed mould, with scraping hymenotome casting solution evenly is coated on the counterdie surface, gelation and dry 48h under room temperature, then at 60-70 ℃ of lower vacuum drying 24h, be soaked in the crosslinker solution gained film crosslinked, remove unreacted impurity with the deionized water cyclic washing at last, drying obtains the cellulose ether hybridized film.
3. the raw material of preparation hybridized film according to claim 1 is characterized in that cellulose ether is methylcellulose, ethyl cellulose, hydroxyethylcellulose or hydroxypropyl cellulose.
4. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 2 is characterized in that the content of ethyl orthosilicate (with respect to cellulose ether) is 0-35wt% among the described step a, does not comprise 0, is preferably 10-25wt%; The mass fraction of cellulose ether aqueous solution is 2-10%, is preferably 4-6%.
5. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 2 is characterized in that, also comprises the pH of solution when regulating teos hydrolysis among the described step a, makes it between 1-3; Gained colloidal sol is filtered through the 2# sand core funnel, remove insoluble matter, leave standstill, deaeration gets casting solution.
6. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 2 is characterized in that mould is any in glass mold, the polytetrafluoroethylene (PTFE) mould among the described step b.
7. the preparation method of the infiltration evaporation hybridized film for separating of methanol aqueous solution according to claim 2, it is characterized in that, described crosslinking agent be in vulcabond, glutaraldehyde, phosphoric acid or the citric acid one or more, preferably vulcabond, glutaraldehyde.
8. the preparation-obtained infiltration evaporation hybridized film for separating of methanol aqueous solution of the described preparation method of claim 2-7 any one.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879714A (en) * | 2014-11-17 | 2016-08-24 | 天津工业大学 | Anti-pollution hollow fiber ultrafiltration membrane and preparation process thereof |
| CN107921377A (en) * | 2015-08-13 | 2018-04-17 | 旭化成株式会社 | Gas separation membrane |
| CN108786484A (en) * | 2018-06-19 | 2018-11-13 | 贵州永合益环保科技有限公司 | A kind of preparation method of hybridized film |
| CN109966935A (en) * | 2019-04-10 | 2019-07-05 | 重庆工程职业技术学院 | A kind of ethyl cellulose-organic-silicon hybridization film and preparation method thereof |
| CN109966936A (en) * | 2019-04-10 | 2019-07-05 | 重庆工程职业技术学院 | A kind of poly adipate succinic acid ester cross-linked silicone hybridized film and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879714A (en) * | 2014-11-17 | 2016-08-24 | 天津工业大学 | Anti-pollution hollow fiber ultrafiltration membrane and preparation process thereof |
| CN107921377A (en) * | 2015-08-13 | 2018-04-17 | 旭化成株式会社 | Gas separation membrane |
| CN108786484A (en) * | 2018-06-19 | 2018-11-13 | 贵州永合益环保科技有限公司 | A kind of preparation method of hybridized film |
| CN109966935A (en) * | 2019-04-10 | 2019-07-05 | 重庆工程职业技术学院 | A kind of ethyl cellulose-organic-silicon hybridization film and preparation method thereof |
| CN109966936A (en) * | 2019-04-10 | 2019-07-05 | 重庆工程职业技术学院 | A kind of poly adipate succinic acid ester cross-linked silicone hybridized film and preparation method thereof |
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Application publication date: 20130403 |