CN103143269A - Chitosan/cellulose composite separation membrane and preparation method thereof - Google Patents
Chitosan/cellulose composite separation membrane and preparation method thereof Download PDFInfo
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- CN103143269A CN103143269A CN2013100656548A CN201310065654A CN103143269A CN 103143269 A CN103143269 A CN 103143269A CN 2013100656548 A CN2013100656548 A CN 2013100656548A CN 201310065654 A CN201310065654 A CN 201310065654A CN 103143269 A CN103143269 A CN 103143269A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A20/124—Water desalination
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Abstract
The invention discloses a chitosan/cellulose composite separation membrane and a preparation method thereof. The preparation method comprises the following step of: directly dissolving chitosan and cellulose by taking a zinc chloride aqueous solution as a solvent; and carrying out an immersion gel method to prepare the chitosan/cellulose composite separation membrane. The prepared composite separation membrane comprises a microporous membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane or a dense membrane. The chitosan/cellulose composite separation membrane has the thickness of 20-100 mu m and the tensile strength of 30-100MPa, the fatality rate of the chitosan/cellulose composite separation membrane for escherichia coli and staphylococcus aureus are 30-90% and 30-97%, respectively. The preparation method is simple and easy to operate, low in price of raw materials and easy in raw material recycling, environmentally-friendly and free of pollution in the process.
Description
Technical field
The present invention relates to a kind of Chitosan/Cellulose composite separating film and preparation method thereof, belong to the natural polymer field, also belong to chemistry, agricultural, field of environment engineering.
Background technology
The research of membrane separation technique has attracted global concern, has huge potentiality on waste water recovery, drink water purifying, desalinization and separate substance.Yet most of films are all by nonbiodegradable petrochemical materials preparation.These nondegradable plastic materials disturb and have destroyed the ecosystem as disposable.
Renewable resource can be considered the ideal material that film is produced.Cellulose is a kind of natural large biological molecule, through being commonly used to prepare degradable membrane, as patent 02132866.8 and patent 200710021069.2.But the anti-microbial property of cellulose membrane is poor.We know, itself has anti-microbial property shitosan.Some researchs directly mix chitosan powder and cellulose solution to improve the anti-microbial property of cellulosic material by physical method.Although the anti-microbial property of blend film more or less improves, the surface ratio of these films is more coarse.And in the process of commercial applications, the leaching of shitosan is with the anti-microbial property of effect of altitude blend film.Therefore, dissolve simultaneously shitosan and cellulose, utilizing recyclable materials to prepare uniform composite membrane is the key issue of producing.
The previous trifluoroacetic acid that adopts prepares shitosan and cellulosic blend film as solvent.But obvious depolymerization occurs in the chain of two kinds of polymer, and chitosan has also occured deacetylated in regenerative process.Afterwards, the people such as Phisalaphong in the biosynthetic process of Acetobacto xylinum with low-molecular-weight 0.25% to 0.75%(weight/volume) chitosan add culture medium to, prepare chitosan/bacteria cellulose composite membrane.But added on the water transfer rate, average crystallite exponential sum anti-microbe ability of the film of shitosan and only had small improvement.Simultaneously while dissolving cellulos and the shitosan in N-methylmorpholine-N-oxide (NMMO) such as Shih prepared transparent blend film.But when the content of chitosan surpasses 5%(w/w's) time, film becomes coarse owing to being separated.In addition, the mixed solution of NaOH/thiocarbamide also can prepare the Chitosan/Cellulose composite membrane.But the operating condition in this dissolution system is very harsh.For example, the temperature of solution should be maintained at about under-12 ℃ in course of dissolution.Recently, ionic liquid, as 1,3-dimethylimidazolium chloride(DMImCl), butyl-3-methylimidazolium acetate(BMIMAc), with 1-H-3-methylimidazolium chloride(HMImCl), also be used to prepare the Chitosan/Cellulose composite membrane.As patent 20081057372.X, although the film of preparation has good performance, regrettably ionic liquid itself is expensive, and is difficult for reclaiming.
Recently a lot of reports all adopt solder(ing)acid to come dissolving cellulos and derivative thereof.Fortunately, chitosan also dissolves in similar inorganic fused salt hydrate (as AlCl
3And FeCl
3).These hydrated salts are very cheap, and might be used for suitability for industrialized production.Also there is not at present report to utilize solder(ing)acid to dissolve simultaneously shitosan and cellulose, and the solution of gained is prepared composite separating film.
Summary of the invention
The object of the present invention is to provide a kind of Chitosan/Cellulose composite separating film and preparation method thereof.This method adopts solder(ing)acid to prepare the Chitosan/Cellulose composite separating film as shitosan and cellulosic cosolvent.This method is simple to operation, the inexpensive easy recovery of raw material, process are environment friendly and pollution-free.
Another object of the present invention is to will preparation the Chitosan/Cellulose composite separating film be applied to that water treatment (comprising sewage disposal, water-oil separating or seawater desalination etc.), protein solution separation, haemodialysis, solution are concentrated, film absorbs or extraction in liquid mixture separation recovery etc. or be used for the recovery that separates of gas separation, infiltration evaporation and gas.
For achieving the above object, the present invention adopts following technical scheme: a kind of Chitosan/Cellulose composite separating film of the present invention is characterized in that: adopting solder(ing)acid is after solvent directly dissolves shitosan and cellulose, makes through immersing gel method; Its concrete grammar comprises the following steps:
Utilize shitosan and cellulose to be prepared into casting solution;
It is asymmetric membrane that described casting solution is immersed gel;
To obtain the Chitosan/Cellulose composite separating film after described asymmetric membrane washing drying.
The described concrete steps of utilizing shitosan and cellulose to be prepared into casting solution comprise: 1) shitosan and cellulose are dissolved in and are prepared into casting solution in solder(ing)acid;
2) shitosan in step 1) and cellulosic total mass fraction are preferably 3% ~ 6%;
3) shitosan in described step 1) and cellulosic material quality mark are than being preferably 1:4 ~ 1:10 for Chitosan/Cellulose.Certainly the metering of this area routine is also available, but effect does not have preferred amounts of the present invention than effective.
It is that the concrete steps of asymmetric membrane comprise that described casting solution is immersed gel:
1) coating machine striking film forming will be used after the preferred evacuation and centrifugal degassing of described casting solution on hot glass sheet;
2) the knifing speed of described coating machine is preferably 2mms
-1~ 10mms
-1
3) film that step 1) is obtained immerses rapidly water/acid/alkali coagulating bath number minute, fully obtains asymmetric membrane, the preferred water coagulating bath after gel.
The described concrete steps that described asymmetric membrane washing drying is obtained the Chitosan/Cellulose composite separating film are:
Described washing is preferably as follows method: first use running water, and rear fully clean with the distilled water washing;
It is 45% ~ 90% that described dry environment is preferably relative humidity, and temperature is 20 ~ 40 ℃.
The most preferred method of described the present invention is characterized in that, with a certain amount of ZnCl
2Be dissolved in and be made into ZnCl in deionized water
2The aqueous solution, then add shitosan and cellulose to form mixture, the mass fraction that shitosan and cellulosic amount account for amount of the mixture is 3% ~ 6% shitosan and cellulose, the mass fraction of described gross mass mark Raw is 1:4 ~ 1:10 than the ratio for shitosan and cellulose, at 70 ℃ ~ 90 ℃ lower rapid stirrings, mixture becomes uniform solution gradually; With after the mentioned solution evacuation and centrifugal degassing on hot glass sheet the striking film forming, then immersed rapidly in water/acid/alkali coagulating bath 1 ~ 20 minute, obtain asymmetric membrane; The asymmetric film of new system is washed away residual solvent with mobile running water and deionized water; Be that 25 ℃, relative humidity are to dry under 85% condition in temperature, namely get the Chitosan/Cellulose composite separating film.
Described shitosan can be the conventional product that uses in this area, but preferred relative molecular mass is 200,000 ~ 400,000, and its deacetylation is the product better effects if of 75 ~ 90 %;
Described cellulosic material, can adopt arbitrarily the conventional fibre element product of this area, as one or more mixing in wood pulp, cotton pulp, jute pulp, bamboo pulp, rice straw pulp, bagasse pulp, mulberry root bark pulp or the reed pulp dregs of rice etc., preferred wood pulp, cotton pulp, jute pulp, bamboo pulp etc., more preferably content of cellulose 〉=90 % wherein, the cellulose products of the cellulosic degree of polymerization 〉=200.
The Chitosan/Cellulose composite separating film that preparation method of the present invention makes is characterized in that:
The thickness of described Chitosan/Cellulose composite separating film is 20 μ m-100 μ m, and hot strength is 30 MPa ~ 100 MPa, and 24 h are respectively 30 % ~ 90 % and 30 % ~ 97 % to the fatal rate of Escherichia coli and staphylococcus aureus.
The Chitosan/Cellulose composite separating film that preparation method of the present invention makes, it is characterized in that: the Chitosan/Cellulose composite separating film has dense film, microfiltration membranes, milipore filter, NF membrane and reverse osmosis membrane, microfiltration membranes, milipore filter, NF membrane and reverse osmosis membrane should be able to be applied to mutually to comprise that water treatment, protein solution separate, haemodialysis, solution is concentrated absorb with film or extraction in liquid mixture separate recovery; Described water treatment comprises sewage disposal, water-oil separating or seawater desalination;
Dense film can be applied to the recovery that separates of gas separation, infiltration evaporation and gas.
The present invention changes (0.02 μ m～10 μ m) microfiltration membranes that coagulating bath kind, coagulating bath time or film drying condition can be prepared into, (10nm～100nm) milipore filter, (approximately 1nm) NF membrane or (0.1～1nm) reverse osmosis membrane, can prepare dense film by naturally drying, dense film is applied to the recovery that separates of gas separation, infiltration evaporation and gas.This is the technology that those skilled in the art can realize.
The present invention is dissolved in shitosan and cellulose in solder(ing)acid simultaneously, scrapes the compound separation of film preparation Chitosan/Cellulose.
Its concrete preparation method comprises the following steps:
(1) preparation of casting solution: a certain amount of zinc chloride is dissolved in is made into solder(ing)acid in deionized water, then adding the gross mass mark is that (the material quality fraction scale is respectively Chitosan/Cellulose=1:4 ~ 1:10) for the shitosan of 3 % ~ 6 % and cellulose, rapid stirring at different temperature, mixture become uniform solution gradually;
(2) will use coating machine striking film forming after the mentioned solution evacuation and centrifugal degassing on hot glass sheet, knifing speed is 2 mms
-1~ 10 mms
-1, then immerse rapidly coagulating bath number minute, fully obtain asymmetric membrane after gel;
(3) film is first used washing from the beginning, more fully clean with distilled water, film is taken out.Be that 45 % ~ 65 % and temperature are in 20 ~ 40 ℃ of environment in relative humidity, the dry Chitosan/Cellulose composite separating film that gets.
Characteristics of the present invention are: the invention provides a kind of green solvent-solder(ing)acid that adopts is the method that solvent prepares the Chitosan/Cellulose composite separating film, the film product good biocompatibility that makes, can durable antibiotic, have highly hydrophilicly, mechanical strength is good.In this method, solvent is easy to reclaim, and cost is low.
Advantage of the present invention is: the present invention is directly dissolved shitosan and cellulose by the Chitosan/Cellulose composite separating film that immerses gel method and prepare different shape, difference in functionality, and the simple environmental protection of whole film-forming process is " green " technique.
The specific embodiment
Embodiment one
With 65 g ZnCl
2Be dissolved in and be made into 65 wt% ZnCl in deionized water
2Then the aqueous solution add shitosan (the relative molecular mass M of gross mass mark 4 wt%
wBe 2 * 10
5Da, deacetylation is about 90 %, Zhejiang Province gold shell Biochemie Co., Ltd) and bamboo pulp fiber element (Fujian Shaowu bamboo pulp factory), the material quality fraction scale is shitosan/bamboo pulp fiber element=1:6, at 80 ℃ of lower rapid stirrings, mixture becomes uniform solution gradually.With after the mentioned solution evacuation and centrifugal degassing on hot glass sheet the striking film forming, then immersed rapidly in the water coagulating bath 20 minutes, obtain asymmetric membrane.The asymmetric film of new system is washed away residual solvent with mobile running water and deionized water.Be that 25 ℃, relative humidity are to dry under 85 % conditions in temperature, standby.Composite separating film thickness is 60 μ m, and hot strength is 40 MPa, and 24 h are respectively 75 % and 80 % to the fatal rate of Escherichia coli and staphylococcus aureus.The pure water flux of composite separating film is 13.81 mLcm
-2H
-1
Embodiment two
With 72 g ZnCl
2Be dissolved in and be made into 72 wt% ZnCl in deionized water
2Then the aqueous solution add shitosan (the relative molecular mass M of 4 wt%
wBe 2 * 10
5Da, deacetylation is about 90 %, Zhejiang Province gold shell Biochemie Co., Ltd) and cotton pulp cellulose (chemical fibre factory, Jiujiang), the material quality fraction scale is shitosan/cotton pulp cellulose=1:6, at 80 ℃ of lower rapid stirrings, mixture becomes uniform solution gradually.With after the mentioned solution evacuation and centrifugal degassing on hot glass sheet the striking film forming, then immersed rapidly in the water coagulating bath 20 minutes, obtain asymmetric membrane.The asymmetric film of new system is washed away residual solvent with mobile running water and deionized water.Be that 30 ℃, relative humidity are to dry under 70 % conditions in temperature, standby.Composite separating film thickness is 50 μ m, and hot strength is 60MPa, and 24h is respectively 73 % and 81 % to the fatal rate of Escherichia coli and staphylococcus aureus.The pure water flux of composite separating film is 15.35 mLcm
-2H
-1
Embodiment three
With 72 g ZnCl
2Be dissolved in and be made into 72 wt%ZnCl in deionized water
2Then the aqueous solution add shitosan (the relative molecular mass M of 4 wt%
wBe 2 * 10
5Da, deacetylation is about 90 %, Zhejiang Province gold shell Biochemie Co., Ltd) and ramee element (Hebei lucky ligusticumic chemical fibre Co., Ltd), the material quality fraction scale is shitosan/ramee element=1:6, at 80 ℃ of lower rapid stirrings, mixture becomes uniform solution gradually.With after the mentioned solution evacuation and centrifugal degassing on hot glass sheet the striking film forming, then immersed rapidly in the water coagulating bath 20 minutes, obtain asymmetric membrane.The asymmetric film of new system is washed away residual solvent with mobile running water and deionized water.Be that 30 ℃, relative humidity are to dry under 60 % conditions in temperature, standby.Composite separating film thickness is 55 μ m, and hot strength is 50 MPa, and 24 h are respectively 80 % and 92 % to the fatal rate of Escherichia coli and staphylococcus aureus.The pure water flux of composite separating film is 16.24 mLcm
-2H
-1
Claims (8)
1. the preparation method of a Chitosan/Cellulose composite separating film is characterized in that: adopting solder(ing)acid is after solvent directly dissolves shitosan and cellulose, makes through immersing gel method; Its concrete grammar comprises the following steps:
Utilize shitosan and cellulose to be prepared into casting solution;
It is asymmetric membrane that described casting solution is immersed gel;
To obtain the Chitosan/Cellulose composite separating film after described asymmetric membrane washing drying.
2. method according to claim 1, is characterized in that, the described concrete steps of utilizing shitosan and cellulose to be prepared into casting solution comprise: 1) shitosan and cellulose are dissolved in and are prepared into casting solution in solder(ing)acid;
2) shitosan in step 1) and cellulosic total mass fraction are 3% ~ 6%;
3) shitosan in described step 1) and cellulosic material quality mark are than being Chitosan/Cellulose=1:4 ~ 1:10.
3. method according to claim 1, is characterized in that, it is that the concrete steps of asymmetric membrane comprise that described casting solution is immersed gel:
1) coating machine striking film forming will be used after described casting solution evacuation and centrifugal degassing on hot glass sheet;
2) the knifing speed of described coating machine is 2mms
-1~ 10mms
-1
3) film that step 1) is obtained immerses rapidly water/acid/alkali coagulating bath number minute, fully obtains asymmetric membrane after gel.
4. according to claim 1 and 2 or 3 described methods, is characterized in that, the described concrete steps that described asymmetric membrane washing drying is obtained the Chitosan/Cellulose composite separating film are:
Described washing methods is: first use running water, and rear fully clean with the distilled water washing;
It is 45% ~ 90% that described dry environment is specially relative humidity, and temperature is 20 ~ 40 ℃.
5. method according to claim 4, is characterized in that, with a certain amount of ZnCl
2Be dissolved in and be made into ZnCl in deionized water
2The aqueous solution, then add shitosan and cellulose to form mixture, the mass fraction that shitosan and cellulosic amount account for amount of the mixture is 3% ~ 6% shitosan and cellulose, the mass fraction of described gross mass mark Raw is 1:4 ~ 1:10 than the ratio for shitosan and cellulose, at 70 ℃ ~ 90 ℃ lower rapid stirrings, mixture becomes uniform solution gradually; With after the mentioned solution evacuation and centrifugal degassing on hot glass sheet the striking film forming, then immersed rapidly in water/acid/alkali coagulating bath 1 ~ 20 minute, obtain asymmetric membrane; The asymmetric film of new system is washed away residual solvent with mobile running water and deionized water; Be that 25 ℃, relative humidity are to dry under 85% condition in temperature, namely get the Chitosan/Cellulose composite separating film.
6. according to claim 1 ~ 4 arbitrary described methods is characterized in that:
Its relative molecular mass of described shitosan is 200,000 ~ 400,000, and its deacetylation is 75 ~ 90 %;
Described cellulosic material adopts one or more mixing in wood pulp, cotton pulp, jute pulp, bamboo pulp, rice straw pulp, bagasse pulp, mulberry root bark pulp or the reed pulp dregs of rice, content of cellulose 〉=90 % wherein, the cellulosic degree of polymerization 〉=200.
7. Chitosan/Cellulose composite separating film that is made by the described preparation method of the arbitrary claim of claim 1-5 is characterized in that:
The thickness of described Chitosan/Cellulose composite separating film is 20 μ m-100 μ m, and hot strength is 30 MPa ~ 100 MPa, and 24 h are respectively 30 % ~ 90 % and 30 % ~ 97 % to the fatal rate of Escherichia coli and staphylococcus aureus.
8. Chitosan/Cellulose composite separating film that is made by the described preparation method of the arbitrary claim of claim 1-5 is characterized in that:
The Chitosan/Cellulose composite separating film has dense film, microfiltration membranes, milipore filter, NF membrane and reverse osmosis membrane, microfiltration membranes, milipore filter, NF membrane and reverse osmosis membrane should be able to be applied to mutually to comprise that water treatment, protein solution separate, haemodialysis, solution is concentrated absorb with film or extraction in liquid mixture separate recovery; Described water treatment comprises sewage disposal, water-oil separating or seawater desalination;
Dense film can be applied to the recovery that separates of gas separation, infiltration evaporation and gas.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399988A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Preparation method for cellulose/chitosan composite modified degradable antibacterial membrane |
| CN105498709A (en) * | 2015-12-16 | 2016-04-20 | 郑州大学 | High-strength dialdehyde microfibrillar cellulose/chitosan composite membrane and preparation method and application thereof |
| CN106237875A (en) * | 2016-08-18 | 2016-12-21 | 福建农林大学 | A kind of preparation method of cellulose base cation selective filter membrane and products thereof |
| CN106660835A (en) * | 2014-08-19 | 2017-05-10 | 栗田工业株式会社 | Reverse osmosis membrane device and method for operating same |
| CN107427780A (en) * | 2015-03-24 | 2017-12-01 | 帝人株式会社 | The manufacture method of composite membrane |
| CN107754619A (en) * | 2017-11-12 | 2018-03-06 | 韦韬 | A kind of preparation method of natural polyelectrolyte NF membrane |
| CN108031312A (en) * | 2017-12-25 | 2018-05-15 | 福建农林大学 | A kind of nanofiltration membrane preparation method combined based on LBL self-assembly with spray-on process |
| CN108465377A (en) * | 2018-02-26 | 2018-08-31 | 福建工程学院 | A kind of preparation method of regenerated cellulose/chitosan composite antibiotic NF membrane |
| CN110026098A (en) * | 2019-04-24 | 2019-07-19 | 中原工学院 | A kind of chitosan hemodialysis membrane and preparation method thereof |
| CN111495207A (en) * | 2020-04-23 | 2020-08-07 | 北京赛诺膜技术有限公司 | Hydrophilic modification method of polymer ultrafiltration membrane |
| WO2020237155A1 (en) * | 2019-05-22 | 2020-11-26 | University Of South Florida | Chitosan based membrane and associated method of use |
| CN112426898A (en) * | 2020-11-06 | 2021-03-02 | 福建农林大学 | Preparation method of antibacterial cellulose flat nanofiltration membrane |
| CN117482759A (en) * | 2023-11-10 | 2024-02-02 | 浙江大学绍兴研究院 | Biomass-based nanofiltration membrane, preparation method and application |
| CN117732245A (en) * | 2023-12-25 | 2024-03-22 | 浙江大学 | Degradable positively charged nanofiltration composite membrane and preparation method and application thereof |
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| CN106660835A (en) * | 2014-08-19 | 2017-05-10 | 栗田工业株式会社 | Reverse osmosis membrane device and method for operating same |
| CN107427780A (en) * | 2015-03-24 | 2017-12-01 | 帝人株式会社 | The manufacture method of composite membrane |
| CN107427780B (en) * | 2015-03-24 | 2021-02-09 | 帝人株式会社 | Method for producing composite film |
| CN105399988A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Preparation method for cellulose/chitosan composite modified degradable antibacterial membrane |
| CN105498709A (en) * | 2015-12-16 | 2016-04-20 | 郑州大学 | High-strength dialdehyde microfibrillar cellulose/chitosan composite membrane and preparation method and application thereof |
| CN106237875A (en) * | 2016-08-18 | 2016-12-21 | 福建农林大学 | A kind of preparation method of cellulose base cation selective filter membrane and products thereof |
| CN107754619B (en) * | 2017-11-12 | 2020-05-19 | 韦韬 | Preparation method of natural polyelectrolyte nanofiltration membrane |
| CN107754619A (en) * | 2017-11-12 | 2018-03-06 | 韦韬 | A kind of preparation method of natural polyelectrolyte NF membrane |
| CN108031312A (en) * | 2017-12-25 | 2018-05-15 | 福建农林大学 | A kind of nanofiltration membrane preparation method combined based on LBL self-assembly with spray-on process |
| CN108465377B (en) * | 2018-02-26 | 2021-01-26 | 福建工程学院 | Preparation method of regenerated cellulose/chitosan composite antibacterial nanofiltration membrane |
| CN108465377A (en) * | 2018-02-26 | 2018-08-31 | 福建工程学院 | A kind of preparation method of regenerated cellulose/chitosan composite antibiotic NF membrane |
| CN110026098A (en) * | 2019-04-24 | 2019-07-19 | 中原工学院 | A kind of chitosan hemodialysis membrane and preparation method thereof |
| CN110026098B (en) * | 2019-04-24 | 2021-08-27 | 中原工学院 | Chitosan hemodialysis membrane and preparation method thereof |
| WO2020237155A1 (en) * | 2019-05-22 | 2020-11-26 | University Of South Florida | Chitosan based membrane and associated method of use |
| CN111495207A (en) * | 2020-04-23 | 2020-08-07 | 北京赛诺膜技术有限公司 | Hydrophilic modification method of polymer ultrafiltration membrane |
| CN112426898A (en) * | 2020-11-06 | 2021-03-02 | 福建农林大学 | Preparation method of antibacterial cellulose flat nanofiltration membrane |
| CN117482759A (en) * | 2023-11-10 | 2024-02-02 | 浙江大学绍兴研究院 | Biomass-based nanofiltration membrane, preparation method and application |
| CN117732245A (en) * | 2023-12-25 | 2024-03-22 | 浙江大学 | Degradable positively charged nanofiltration composite membrane and preparation method and application thereof |
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