CN102806025A - Method for preparing hydrophobic zein film for bioethanol pervaporation separation - Google Patents
Method for preparing hydrophobic zein film for bioethanol pervaporation separation Download PDFInfo
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- CN102806025A CN102806025A CN2012102358680A CN201210235868A CN102806025A CN 102806025 A CN102806025 A CN 102806025A CN 2012102358680 A CN2012102358680 A CN 2012102358680A CN 201210235868 A CN201210235868 A CN 201210235868A CN 102806025 A CN102806025 A CN 102806025A
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Abstract
The invention discloses a method for preparing a hydrophobic zein film for bioethanol pervaporation separation, which takes zein as a main raw material, the zein is dissolved in an ethanol solution of 70%-90%, through regulating the pH value of the solution, under the action of high-speed mixing, zein microsphere casting film liquid is prepared through a phase separation technology. The specific hydrophobicity and good film-forming property of zein are utilized, two zein films with different structures are prepared on the porous base material surfaces of different materials through various coating technologies, and continuous films are then uniformly coated on the zein films densely. The zein film is assembled in a pervaporation device, and is applied in a bioethanol separation technology. The method can be suitable for various coating technologies, and is simple and convenient to operate. The prepared zein supported film can be used for separating and concentrating the ethanol of bioethanol fermentation liquor, so the production cost is lowered. Compared with functional packaging materials and drug controlled release carriers, the zein supported film can be used for broadening the application of the zein supported film in the separation field.
Description
Technical field
The invention belongs to the natural macromolecular material technical field, relate to a kind of preparation method of hydrophobic maize alcohol-soluble protein film specifically and in the application in pervaporation separating bio ethanol field.
Background technology
Zeins (zein) is main corn alcohol karst valley thing albumen, accounts for 40～50% of total protein content, and non-chemically method extracts from the natural corn albumen powder.Its molecular structure is to arrange the alpha-helix that forms with antiparallel manner by nine repetitives; Nonpolar, hydrophobic in a large number amino acid forms amino acid sequence through peptide bond; Being connected with hydrogen bond through disulfide bond again between sequence forms three-dimensional netted peptide chain, and promptly tertiary structure is the spindle shape.The nonpolar amino acid of high-load, acid and basic amino acid lacks the special dissolubility that has determined it, and promptly Zein was both water insoluble, also was insoluble to absolute ethyl alcohol, only dissolved in 50%～90% ethanol/water solution.Generally speaking; It has unique dissolution characteristics, hear resistance, film forming, hydrophobicity, biocidal property and non-oxidizability; Can be used for protection against the tide, oxygen barrier, uvioresistant, antistatic etc., so its research and development have become the research focus of new bio base polymeric material.Based on its good hydrophobicity, degradability and film forming, be widely used in degradable packaging material for food field; Based on its special solubility behavior, form microsphere through phase disengagement method, overseas utilization zein microballoon is applied to as carrier that medicine is slow, the controlled release field.
Bio-ethanol is expected to substitute the clean fuel that fossil fuel uses, its wide material sources as a kind of potential.The zymotechnique production bio-ethanol new technology of a large amount of human and material resources development and use starch based, cellulose family and living beings etc. is all dropped in countries in the world at present.In the traditional handicraft, the tunning of the bio-ethanol i.e. ethanolic solution of 3～5wt% separates through distil process, and it is bigger to consume energy.For cutting down the consumption of energy, adopt the pervaporation membrane separation technique to carry out the separation of azeotropic mixture ethanol/water.The bottleneck of its technological development is the design and the preparation of hydrophobic type ethanol diffusion barrier.For this reason, various hydrophobic membrane materials are studied and develop, and comprise polymer film, zeolite molecular sieve film and hybrid organic-inorganic film etc.Through pervaporation, can the ethanolic solution of 3～5wt% be carried dense to 30wt.%.In actual production, installation for fermenting usually is coupled with the pervaporation separator, thus the continuous production that has realized bio-ethanol with separate, can in time separate on the one hand has inhibiting ethanol component to sweat, realizes high efficiency; On the other hand, cut down the consumption of energy effectively, can reduce the production cost of bio-ethanol.The used zeins raw material of the present invention is the accessory substance in the bio-ethanol industry exactly, produces approximately recyclable 1.3 ten thousand tons of zein accessory substances of 5,000 ten thousand liters of ethanol.Up to now, do not find to utilize the related patent U.S. Patent No. and the document of zein film separating alcohol/aqueous solution as yet.
Chinese patent N1001318 provides a kind of maize alcohol-soluble protein film that in food, medicine packing, uses and can in natural environment, degrade fully and preparation method thereof; This preparation method needs heating operation; Need frozen water; And need on extruder, push film forming, be mainly used in food, the use of pharmaceutical packing material.
Summary of the invention
In order to solve the problem that exists in the prior art, the present invention provides a kind of preparation method of hydrophobic maize alcohol-soluble protein film, and it is narrow to solve bio-ethanol separation membrane material range of choice, and cost is high, the problem of existing hydrophobic maize alcohol-soluble protein film complicated process of preparation.
Technical scheme of the present invention is following: a kind of preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol; Under the high-speed stirred effect; Prepare the microballoon casting solution through phase separation process, coating filmform on porous substrate, its processing step is following:
(1) one to multiple part of zeins powder is dissolved in respectively in the ethanol water, forms former protein solution, and ultrasonic 5-10min;
(2) the former protein solution that obtains in the step (1) is transferred in the there-necked flask that is connected with high-speed stirring apparatus; PH value to 8～10 with NaOH solution regulator solution system; High-speed stirred 3～5min adds distilled water in the process that continues to stir, and the ethanol volume fraction in the control final solution;
(3) casting solution that obtains in the step (2) is coated with membrane technology through difference, carries out tunicle on the porous substrate surface of unlike material, after being accomplished by membrane process, at room temperature dry to remove the residual solvent in the film.
The concentration of ethanol water is 70%～90% in the said step (1).
Said step (1) Central Plains protein solution refers to 5～100mgzein/mL ethanol water.
The high-speed stirring apparatus of said step (2) is a laboratory dispersion and emulsion homogenizer, and mixing speed is 5,000～15,000rpm.
Ethanol volume fraction in the final solution of said step (2) is controlled at 30%～40%.
The different membrane technology that is coated with in the said step (3) refers to The tape casting, dip-coating method, vacuum filtration method or spin-coating method.
The porous substrate of the unlike material in the said step (3) refers to porous metal film pipe or diaphragm, Kynoar (PVDF) milipore filter material, cellular PVC (PVC) film material, Woelm Alumina (α-Al
2O
3) ceramic-film tube or diaphragm or porous silica (SiO
2) the ceramic membrane material.
Tunicle comprises continuous film (ZS) and two kinds of films of ball film compounded double-layer film (ZC) of even structure in the said step (3), and film forming preparation technology is different, and wherein the ZS film is to process with the casting solution tunicle 6 times of 80～100mg/mL stoste preparation; And the ZC film is the microballoon casting solution tunicle that makes with the stoste of 10～30mg/mL earlier 3 times, and the casting solution that the back prepares with 80～100mg/mL stoste is coated with 3 times and processes.
The coating process of said step (3) operates in 1000 clean levels, and humidity is 50%, accomplishes under the space environment that temperature is 25 ℃.
The application of a kind of hydrophobic maize alcohol-soluble protein film in pervaporation separating bio ethanol.
Technical scheme of the present invention is a primary raw material with the zeins, is dissolved in 70%～90% the ethanolic solution, and through the pH value of regulator solution, (5,000～15,000rpm) effect prepares zein microballoon casting solution through phase detachment technique down in high-speed stirred.The addition of distilled water can prepare dissimilar casting solutions in concentration through control zein solution and the phase separation process.By distinctive hydrophobicity of zein and good film forming; Be coated with membrane technology goes out two kinds of different structures in the porous substrate surface preparation of unlike material maize alcohol-soluble protein film through multiple; Be continuous film (ZS) or ball film compounded double-layer film (ZC), two types of thicknesses of layers all can be controlled in about 10 μ m.The design feature of ball film compounded double-layer film, the uniform microsphere that promptly on porous substrate, at first prepares by particle diameter 1～2 μ m piles up the ball rete that forms, and evenly applies fine and close continuous rete more above that.And it is assembled in the pervaporation device, be applied to the separating technology of bio-ethanol.The preparation method's advantage that is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol provided by the invention is:
1. applicable to multiple coating process (like The tape casting, dip-coating method, spin-coating method etc.), simple, convenient.
2. can go up preparation zein supported film at different porous substrates (metal, pottery and macromolecular material).
3.zein thicknesses of layers is even, controlled, quality of forming film is good, is applicable to large tracts of land film forming or special-shaped base material film forming.
4.zein film preparation technology and zein film pervasion evaporation isolation technics is all simple to operate, cost is low, pollution-free.
5. prepared zein supported film can be realized the ethanol separation of bio-ethanol zymotic fluid and concentrate, reduce production costs.
6. with respect to functional packing material and slow releasing carrier of medication, the zein supported film has been widened its application at separation field.
The specific embodiment
For the present invention is described better, the practical implementation case is following:
Embodiment 1
With 0.5g zeins powder dissolution in the ethanol water of 50mL70% (v/v), form former protein solution a, 4g zeins powder dissolution forms former albumen and dissolves b and ultrasonic 5min in the ethanol water of 50mL70% (v/v).
2. the former protein solution a, the b that obtain in the step 1 are transferred to respectively in the there-necked flask that is connected with high-speed stirring apparatus; PH value to 10 with the NaOH solution regulator solution of 1mol/L; Control high-speed stirred speed 5,000rpm is behind the stirring 5min; Respectively 50mL distilled water is slowly splashed in the solution at stirring condition again, obtain corresponding casting solution a, b.
3. adopt dip-coating method to be coated with membrane technology the casting solution that obtains in the step 2 is coated in pretreated Woelm Alumina (α-Al
2O
3) substrate surface.Two kinds of films (ZS and ZC) film-forming process of lining is different, directly porous carrier is flooded to lift 6 times and process the ZS film in casting solution b; And ZC film film-forming process is: at first porous carrier is flooded to lift in casting solution a and forms the ball rete for 3 times, leave standstill 20min after, dipping lifts 3 times and forms continuous rete in casting solution b again.Be coated with that membrane process is 50% in 1000 clean levels, humidity, carry out in the environment of 25 ℃ of temperature, after being accomplished by membrane process, at room temperature dry 24h is to remove the residual solvent in the film.
4. ZS and ZC film are assembled in respectively in the pervaporation device, separate 3% ethanol water under the room temperature, the permeation flux J of ZS film is 0.69kg.m
-2.h
-1, ethanol separation α
E/WReach 3.31, and the permeation flux J of ZC film and ethanol separation factor alpha
E/WBe respectively 0.71kg.m
-2.h
-1With 3.45.Gas infiltration (N before and after the pervaporation experiment
2) experimental result shows that film is all airtight, i.e. the complete non-structure defective of film.
Embodiment 2
With 1g zeins powder dissolution in the ethanolic solution of 50mL 80% (v/v), form former protein solution a, 4.5g zeins powder dissolution forms former albumen and dissolves b and ultrasonic 5min in the ethanol water of 50mL80% (v/v).
2. the former protein solution a, the b that obtain in the step 1 are transferred to respectively in the there-necked flask that is connected with high-speed stirring apparatus; PH value to 10 with the NaOH solution regulator solution of 1mol/L; Control high-speed stirred speed 5,000rpm is behind the stirring 5min; Respectively 50mL distilled water is slowly splashed in the solution at stirring condition again, obtain corresponding casting solution a, b.
3. adopt The tape casting that the casting solution that obtains in the step 2 is coated on pretreated polyvinyl chloride (PVC) porous substrates surface.Two kinds of films (ZS and ZC) film-forming process of lining is different, utilizes casting solution b, with polyvinyl chloride porous substrates tunicle 6 times preparation ZS film repeatedly on casting machine; The moulding of ZC film The tape casting then utilizes casting solution a tunicle 3 times earlier, leaves standstill behind the 20min casting solution b tunicle 3 times again.Be coated with that membrane process is 50% in 1000 clean levels, humidity, carry out in the environment of 25 ℃ of temperature, after being accomplished by membrane process, at room temperature dry 24h is to remove the residual solvent in the film.
4. above-mentioned ZS and ZC film are assembled in the pervaporation device; Separate 3% ethanol water under the room temperature, reach the pervaporation experiment of 120h, operate forward and backward pure gas permeability test and show; The rete of ZS film and ZC film is all airtight, explains that rete is complete, the non-structure defective.The permeation flux J of ZS film is 0.65kg.m
-2.h
-1, the ethanol separation factor alpha
E/WReach 3.56, and the separating property of ZC film is respectively 0.69kg.m
-2.h
-1With 3.77.
Embodiment 3
With 5g zeins powder dissolution in the ethanol water of 50mL90% (v/v), form former protein solution, and ultrasonic 5min.
2. the former protein solution that obtains in the step 1 is transferred in the there-necked flask that is connected with high-speed stirring apparatus; PH value to 10 with the NaOH solution regulator solution of 1mol/L; Control high-speed stirred speed 10,000rpm is behind the stirring 5min; 80mL distilled water is slowly splashed in the solution at stirring condition, obtain corresponding casting solution.
3. adopt spin coating technique that the casting solution that obtains in the step 2 is coated on the pretreated porous silica substrate.Spin coating is 6 times repeatedly, forms the ZS film.Be coated with that membrane process is 50% in 1000 clean levels, humidity, carry out in the space of 25 ℃ of temperature, after being accomplished by membrane process, at room temperature dry 24h is to remove the residual solvent in the film.
4. above-mentioned ZS film is assembled in the pervaporation device, is used for separating 5% ethanol water under the normal temperature, and permeation flux J is 0.80kg.m
-2.h
-1, ethanol separation α
E/WReach 3.25.Every pervaporation 12h, rete reuse 6～8 times after by 50 ℃ of vacuum drying, and performance does not have obvious decay.
Embodiment 4
With 1.5g zeins powder dissolution in the ethanol water of 50mL70% (v/v), form former protein solution a, 5.0g zeins powder dissolution forms former albumen and dissolves b and ultrasonic 5min in the ethanol water of 50mL70% (v/v).
2. with the former protein solution a that obtains in the step 1, b transfers to respectively in the there-necked flask that is connected with high-speed stirring apparatus, with the pH value to 10 of the NaOH solution regulator solution of 1mol/L; Control high-speed stirred speed 10; 000rpm behind the stirring 5min, slowly splashes in solution at stirring condition 50mL distilled water respectively; Obtain corresponding casting solution a, b.
3. adopt spin coating technique the casting solution that obtains in the step 2 to be coated on the surface of pretreated Kynoar (PVDF) ultrafiltration diaphragm.Two kinds of films (ZS and ZC) film-forming process of lining is different, utilizes casting solution b, with polyvinylidene fluoride (PVDF) ultrafiltration membrane sheet tunicle 6 times preparation ZS film repeatedly on whirler; The moulding of ZC film spin-coating method then utilizes casting solution a tunicle 3 times earlier, leaves standstill behind the 20min casting solution b tunicle 3 times again.Be coated with that membrane process is 50% in 1000 clean levels, humidity, carry out in the environment of temperature 25C, after being accomplished by membrane process, at room temperature dry 24h is to remove the residual solvent in the film.
4. above-mentioned ZS film is assembled in the pervaporation device, is used for separating 5% ethanol water under the normal temperature, and permeation flux J is 0.72kg.m
-2.h
-1, ethanol separation α
E/WReach 3.66.The permeation flux J of ZC film and ethanol separation α
E/WBe respectively 0.97kg.m
-2.h
-1With 3.93.After the rete preparation, air ambient is placed the back use of 1 week, and the pervaporation performance is with just preparation back result of use is suitable.
Embodiment 5
With 5g zeins powder dissolution in the ethanol water of 50mL70% (v/v), form former protein solution, and ultrasonic 5min.
2. the former protein solution that obtains in the step 1 is transferred in the there-necked flask that is connected with high-speed stirring apparatus; PH value to 10 with the NaOH solution regulator solution of 1mol/L; Control high-speed stirred speed 15,000rpm is behind the stirring 5min; 40mL distilled water is slowly splashed in the solution at stirring condition, obtain corresponding casting solution.
3. adopt the dipping technology of lifting that the casting solution that obtains in the step 2 is coated on the outer surface of pretreated porous metal film pipe.Lift repeatedly 6 times, form the ZS film.Be coated with that membrane process is 50% in 1000 clean levels, humidity, carry out in the space of 25 ℃ of temperature, after being accomplished by membrane process, at room temperature dry 24h is to remove the residual solvent in the film.
4. above-mentioned ZS film is assembled in the pervaporation device, is used for separating 1% ethanol water under the normal temperature, and permeation flux J is 1.20kg.m
-2.h
-1, ethanol separation α
E/WReach 5.02.Pervaporation 120h, the separating property attenuation degree of rete is little.Consider the expensive of film material, the film material behind the tunicle after 600 ℃ of calcinings, still can be done porous carrier and reused.
Although the present invention has been carried out foregoing description; But the present invention is not limited to the above-mentioned specific embodiment, and the above-mentioned specific embodiment only is schematically, rather than restrictive; Those of ordinary skill in the art is under enlightenment of the present invention; Under the situation that does not break away from aim of the present invention and claim institute protection domain, can also make a lot of distortion, these all belong to the row of protection of the present invention.
Claims (10)
1. the preparation method as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol is characterized by under the high-speed stirred effect, prepares the microballoon casting solution through phase separation process, coating filmform on porous substrate, and its processing step is following:
(1) one to multiple part of zeins powder is dissolved in respectively in the ethanol water, forms former protein solution, and ultrasonic 5-10min;
(2) the former protein solution that obtains in the step (1) is transferred in the there-necked flask that is connected with high-speed stirring apparatus; PH value to 8～10 with NaOH solution regulator solution system; High-speed stirred 3～5min adds distilled water in the process that continues to stir, and the ethanol volume fraction in the control final solution;
(3) casting solution that obtains in the step (2) is coated with membrane technology through difference, carries out tunicle on the porous substrate surface of unlike material, after being accomplished by membrane process, at room temperature dry to remove the residual solvent in the film.
2. the preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol according to claim 1 is characterized in that the concentration of ethanol water is 70%～90% in the said step (1).
3. the preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol according to claim 1 is characterized in that, said step (1) Central Plains protein solution refers to 5～100mgzein/mL ethanol water.
4. the preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol according to claim 1; It is characterized in that the high-speed stirring apparatus of said step (2) is a laboratory dispersion and emulsion homogenizer, mixing speed is 5; 000～15,000rpm.
5. the preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol according to claim 1 is characterized in that the ethanol volume fraction in the final solution of said step (2) is controlled at 30%～40%.
6. the preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol according to claim 1; It is characterized in that the different membrane technology that is coated with in the said step (3) refers to The tape casting, dip-coating method, vacuum filtration method or spin-coating method.
7. the preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol according to claim 1; It is characterized in that the porous substrate of the unlike material in the said step (3) refers to porous metal film pipe or diaphragm, polyvinylidene fluoride (PVDF) ultrafiltration membrane material, cellular PVC film material, porous alumina ceramic film pipe or diaphragm or porous silica ceramic membrane material.
8. the preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol according to claim 1; It is characterized in that; Tunicle comprises ZS and two kinds of films of ZC in the said step (3); Film forming preparation technology is different, and wherein the ZS film is to process with the casting solution tunicle 6 times of 80～100mg/mL stoste preparation; And the ZC film is the microballoon casting solution tunicle that makes with the stoste of 10～30mg/mL earlier 3 times, and the casting solution that the back prepares with 80～100mg/mL stoste is coated with 3 times and processes.
9. the preparation method who is used as the hydrophobic maize alcohol-soluble protein film of pervaporation separating bio ethanol according to claim 1; It is characterized in that; The coating process of said step (3) operates in 1000 clean levels, and humidity is 50%, accomplishes under the space environment that temperature is 25 ℃.
10. the application of hydrophobic maize alcohol-soluble protein film in pervaporation separating bio ethanol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108975722A (en) * | 2018-06-11 | 2018-12-11 | 福州市长乐区三互信息科技有限公司 | A kind of hydrophobic automobile adhesive film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302550A (en) * | 2000-01-01 | 2001-07-11 | 天津商学院 | Process for preparing alcohol-soluble corn protein membrane from corn gluten |
-
2012
- 2012-07-09 CN CN2012102358680A patent/CN102806025A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302550A (en) * | 2000-01-01 | 2001-07-11 | 天津商学院 | Process for preparing alcohol-soluble corn protein membrane from corn gluten |
Non-Patent Citations (2)
| Title |
|---|
| YALU MA, ET AL.: "Preparation of zein-based membranes and their pervaporation for ethanol aqueous solution", 《DESALINATION》, vol. 299, 18 June 2012 (2012-06-18), pages 70 - 78, XP028499082, DOI: doi:10.1016/j.desal.2012.05.024 * |
| 贾佩楠 等: "生物乙醇提浓工艺中渗透蒸发膜材料的研究进展", 《化学工业与工程》, vol. 29, no. 3, 31 May 2012 (2012-05-31), pages 60 - 65 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108975722A (en) * | 2018-06-11 | 2018-12-11 | 福州市长乐区三互信息科技有限公司 | A kind of hydrophobic automobile adhesive film and preparation method thereof |
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Application publication date: 20121205 |