CN104275094A - Chitosan quaternary ammonium HTCC/polyethersulfone composite nanofiltration membrane and preparation - Google Patents

Chitosan quaternary ammonium HTCC/polyethersulfone composite nanofiltration membrane and preparation Download PDF

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Publication number
CN104275094A
CN104275094A CN201310285981.4A CN201310285981A CN104275094A CN 104275094 A CN104275094 A CN 104275094A CN 201310285981 A CN201310285981 A CN 201310285981A CN 104275094 A CN104275094 A CN 104275094A
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htcc
chitosan
quaternary ammonium
composite membrane
ammonium salt
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CN201310285981.4A
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黄中华
刘郑丽
朱立君
古丽米拉·艾克拜尔
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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Abstract

The invention provides a preparation method of a chitosan quaternary ammonium HTCC/polyethersulfone (PES) positively charged composite nanofiltration membrane. According to the preparation method, positively charged 2-hydroxypropyltrimethyl ammonium chloride chitosan (HTCC) is used as a surface-active functional layer, a polyethersulfone ultrafilter membrane with good hydrophilic performance is used as a supporting layer, epoxy chloropropane (ECH) is used as a cross-linking agent, and a coating and crosslinking reaction method is adopted to prepare the positively charged chitosan composite nanofiltration membrane. The preparation method has a simple technology and is natural and environmentally friendly. The positively charged composite nanofiltration membrane prepared by the above method has good hydrophilic performance and excellent mechanical property. Water flux under the operating pressure of 0.4 MPa is 4.77-8.96L.m<-2>.h<-1>, and the positively charged composite nanofiltration membrane has high retention rate for organic matters with molecular weight being more than 600 and inorganic salt solutions such as MgCl2 and the like, and can be used for separating and removing micro/trace pollutants, especially positively charged matters.

Description

Quaternary Ammonium Salt of Chitosan HTCC/ polyether sulfone composite nanometer filtering film and preparation thereof
Technical field
The present invention relates to a kind of shitosan Positively charged composite nanofiltration membrane and preparation method thereof, particularly a kind of hydrophily, satisfactory mechanical property, NF membrane that rejection is high and preparation method thereof, belongs to UF membrane field.
Background technology
Nanofiltration is the driving membrane separation technique of a kind of novel pressure between ultrafiltration and counter-infiltration, and its trapped particles size is less than ultrafiltration, and transmitance is larger than counter-infiltration, and operating pressure is low, is developed rapidly in recent ten years.Nanofiltration membrane treatment technology not easily produces toxic by-products, and to molecular mass be 150 ~ 1000 rejection to organics effect better, in removal environment, in trace-organic micro-pollutant, there are potential advantages.But, the commercial NF membrane electricity or neutral in bear mostly at present, nanofiltration membrane with negative electric charge serves good separating effect really to high-valence anion, small organic molecule, but is not very desirable to cation and the organic separating effect of lotus carbonium type.In addition, fouling membrane is also the subject matter of restriction membrane technology commercial applications.
Shitosan is the product of chitin deacetylate, at occurring in nature rich content, has unique biocompatibility, biological degradability, antibiotic property and film forming.Chitosan molecule chain is dispersed with a large amount of hydroxyls (-OH) and amino (-NH 2), the existence of these active groups makes it be easy to carry out derivative modification, and the functional membrane material thus prepared based on Chitosan-phospholipid complex is more and more paid close attention to by people.Chitosan film immerses containing 0.16gNaOH by Hoven etc., in the 10.0mL absolute methanol solution of 0.30gNaI, gradation adds 0.6g iodomethane at 40 DEG C, reacts obtained lotus positive electricity chitosan film, compared with former chitosan film, this film has better Selective adsorption to protein, less to the dependence of pH value, but the swellbility of this film in water is higher, poor (the Hoven V P of mechanical strength, Tangpasuthadol V, Angkitpaiboon Y, Vallapa N and Kiatkamjornwong S. Surface-charged chitosan:Preparation and protein adsorption. Carbohydrate Polymers, 2007, 68 (1): 44-53).Huang etc. take toluene di-isocyanate(TDI) as crosslinking agent, composite algorithm is adopted to prepare modification of chitosan GCTACC/ polyacrylonitrile positively charged nanofiltration membranes, but unsatisfactory (the Huang R H of this film pure water permeability energy, Chen G H, Sun M K and Gao C J. Preparation and characterization of composite NF membrane from a graft copolymer of trimethylallyl ammonium chloride onto chitosan by toluene diisocyanate cross-linking. Desalination, 2009, 239:38-45).For the problems referred to above, the present invention by with the Quaternary Ammonium Salt of Chitosan HTCC of lotus positive electricity for active layer, poly (ether-sulfone) ultrafiltration membrane is supporting layer, coating-crosslinked composite algorithm is adopted to prepare positively charged nanofiltration membranes, this product has good hydrophily, antibiotic property, chemical stability and mechanical performance, can be used for that cation and lotus carbonium type are organic to be separated and in the separation process such as counter-infiltration and pervaporation.
Summary of the invention
The object of the present invention is to provide a kind of shitosan Positively charged composite nanofiltration membrane and preparation method thereof.With the composite membrane that this legal system is standby, there is good hydrophilicity and mechanical performance, to some organic matter and inorganic salts rejection higher, can be used for the separation of pollutant in water environment.
The technical solution realizing the object of the invention is: a kind of Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane, and described composite membrane is the NF membrane of positively charged, with Quaternary Ammonium Salt of Chitosan HTCC for active layer, take poly (ether-sulfone) ultrafiltration membrane as supporting layer.
Described composite membrane is to the MgCl of 1.0g/L 2solution rejection be 73.0%-91.9%, the water flux of described composite membrane is 4.77-8.96Lm -2h -1, the mechanical strength of described composite membrane is 233.24-266.12MPa, and the contact angle of described composite membrane is 62.7 °-63.9 °.
A preparation method for Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane, comprises the following steps:
(1) take refining HTCC sample soluble in water, be made into the casting solution of mass concentration 1.0%-2.0%;
(2) fixed on a glass by poly (ether-sulfone) ultrafiltration membrane, draw casting solution even application on film, the wet film obtained is placed in less than 50 DEG C temperature and flashes to dry film;
(3) configuration quality concentration is the epoxychloropropane ethanolic solution of 1.6%-2.2%, is placed in closed container, adds aqueous slkali;
(4) dry film in step 2 is soaked in the solution in step 3,45-55 DEG C of cross-linking reaction;
(5) after cross-linking reaction, film is taken out 45-55 DEG C of heat treatment, finally by deionized water washing, soak, to be determined.
In step (1), the substitution value of Quaternary Ammonium Salt of Chitosan HTCC is greater than 88.65%.
In step (2), the molecular cut off of poly (ether-sulfone) ultrafiltration membrane is 10000, and effective area is 50.3cm 2.
Aqueous slkali described in step (3) is the potassium hydroxide solution of 50wt%, and described alkali and the amount ratio of ethanol are 4-8mg/mL.
Cross-linking reaction time described in step (4) is not less than 20h.
Heat treatment time described in step (5) is 20-30min.
The present invention compared with prior art, its remarkable advantage: preparation method's technique is simple, natural environmental-protective.Composite nanometer filtering film has good hydrophilicity and mechanical performance, to organic matter and the MgCl of molecular weight more than 600 2higher Deng inorganic salt solution rejection, the separation that can be used for some polluter in water environment is removed.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preparation method of shitosan Positively charged composite nanofiltration membrane of the present invention.
Fig. 2 is the preparation method of shitosan Positively charged composite nanofiltration membrane of the present invention is 1.9% in crosslinking agent mass concentration, and the film of casting solution mass concentration is 1.0%, KOH addition when being 0.3g gained is to organic retention curve figure.
Fig. 3 is the preparation method of shitosan Positively charged composite nanofiltration membrane of the present invention is 1.9% in crosslinking agent mass concentration, and the film of casting solution mass concentration is 1.0%, KOH addition when being 0.3g gained is to the rejection figure of different inorganic salts.
Fig. 4 is the preparation method of shitosan Positively charged composite nanofiltration membrane of the present invention is 1.9% in crosslinking agent mass concentration, casting solution mass concentration is 1.0%, the film of gained and the scanning electron microscope (SEM) photograph of PES basement membrane, wherein a polyether sulfone basement membrane when KOH addition is 0.3g, b composite membrane.
Fig. 5 is the preparation method of shitosan Positively charged composite nanofiltration membrane of the present invention is 1.9% in crosslinking agent mass concentration, casting solution mass concentration is 1.0%, the film of gained and the AFM figure of PES basement membrane, wherein a polyether sulfone basement membrane when KOH addition is 0.3g, b composite membrane.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail.
(1) take refining HTCC sample soluble in water, be made into the casting solution of mass concentration 1.0%-2.0%;
(2) fixed on a glass by poly (ether-sulfone) ultrafiltration membrane, draw casting solution even application on film, the wet film obtained is placed in less than 50 DEG C temperature and flashes to dry film;
(3) configuration quality concentration is the epoxychloropropane ethanolic solution of 1.6%-2.2%, is placed in closed container, adds aqueous slkali;
(4) dry film in step 2 is soaked in the solution in step 3,45-55 DEG C of cross-linking reaction;
(5) after cross-linking reaction, film is taken out 45-55 DEG C of heat treatment, finally by deionized water washing, soak, to be determined.
Embodiment 1: be dissolved in deionized water by a certain amount of refining HTCC sample, be made into the casting solution that mass concentration is 1.0%, draw casting solution even application on 3 poly (ether-sulfone) ultrafiltration membranes respectively, the wet film obtained is placed in less than 50 DEG C temperature and flashes to dry film.Then, 3 dry films are soaked in respectively to fill mass concentration be that in the container of epoxychloropropane ethanolic solution (wherein ethanol is 50mL) of 1.6%, 1.9%, 2.2%, KOH addition is 0.4g, airtight, 45-55 DEG C of more than cross-linking reaction 20h.After cross-linking reaction, film is taken out at 45-55 DEG C of heat treatment 20min-30min.Finally, composite membrane washs through deionized water, is placed in deionized water and soaks more than 24h, to be determined.
3 obtained films are to the MgCl of 1.0g/L 2solution rejection be followed successively by 79.1%, 90.4%, 73.0%, water flux is followed successively by 7.91,7.12,6.96Lm -2h -1, mechanical strength is followed successively by 266.12,243.25,239.89MPa, contact angle is followed successively by 63.1 °, 63.0 °, 63.9 °.
Embodiment 2: refining HTCC sample is dissolved in deionized water, be made into the casting solution that mass concentration is 1.0%, 1.5%, 2.0% respectively, draw appropriate casting solution even application on 3 poly (ether-sulfone) ultrafiltration membranes successively, the wet film obtained is placed in less than 50 DEG C temperature and flashes to dry film.Then, 3 dry films are soaked in respectively to fill mass concentration be that in the container of epoxychloropropane ethanolic solution (wherein ethanol is 50mL) of 1.9%, KOH addition is 0.4g, airtight, 45-55 DEG C of more than cross-linking reaction 20h.After cross-linking reaction, film is taken out at 45-55 DEG C of heat treatment 20min-30min.Finally, composite membrane washs through deionized water, is placed in deionized water and soaks more than 24h, to be determined.
3 obtained films are to the MgCl of 1.0g/L 2solution rejection be followed successively by 90.4%, 87.8%, 81.6%, water flux is followed successively by 7.12,4.77,5.69Lm -2h -1, mechanical strength is followed successively by 234.27,236.56,240.66MPa, contact angle is followed successively by 63.3 °, 63.2 °, 62.7 °.
Embodiment 3: be dissolved in deionized water by a certain amount of refining HTCC sample, be made into the casting solution that mass concentration is 1.0%, draw appropriate casting solution even application on 3 poly (ether-sulfone) ultrafiltration membranes, the wet film obtained is placed in less than 50 DEG C temperature and flashes to dry film.Then, 3 dry films are soaked in respectively to fill mass concentration be that in the container of epoxychloropropane ethanolic solution (wherein ethanol is 50mL) of 1.9%, KOH addition is followed successively by 0.2g, 0.3g, 0.4g, airtight, 45-55 DEG C of more than cross-linking reaction 20h.After cross-linking reaction, film is taken out at 45-55 DEG C of heat treatment 20min-30min.Finally, composite membrane washs through deionized water, is placed in deionized water and soaks more than 24h, to be determined.
3 obtained films are to the MgCl of 1.0g/L 2solution rejection be followed successively by 81.0%, 91.9%, 84.7%, water flux is followed successively by 8.96,8.20,7.86 Lm -2h -1, mechanical strength is followed successively by 239.15,234.53,233.24MPa, contact angle is followed successively by 63.4 °, 63.2 °, 62.9 °.
As seen from the above embodiment, the preparation method of shitosan Positively charged composite nanofiltration membrane of the present invention, by regulating concentration, the concentration of casting solution HTCC, the addition of KOH of crosslinking agent ECH, has inquired into different masking factor to the impact of film properties.When ECH mass concentration be 1.6%-2.2%, HTCC mass concentration be 1.0%-2.0%, KOH addition is 0.2-0.4g, the film of gained is to the MgCl of 1.0g/L 2the rejection of solution, water flux present regular change, and mechanical performance and hydrophilicity are comparatively stable.Composition graphs 2 is known, and the rejection to organics rate of composite membrane to molecular weight more than 600 is higher, and under this experiment condition, the molecular cut off of film is 977, belongs to molecular cut off (200-2000) scope of NF membrane; Composition graphs 3 is known, and composite membrane is to the MgCl of 1.0g/L 2, NaCl, KCl, MgSO 4, Na 2sO 4, K 2sO 4the rejection of solution is successively decreased successively, is respectively 94.5%, 69.8%, 66.7%, 46.9%, 30.4%, 21.1%.The cutoff performance of NF membrane is relevant with the ionic species in solution and existence form, is judged by electrostatic interaction and spatial effect analysis, and what this film presented positively charged nanofiltration membranes retains characteristic; Composition graphs 4 is known, in the resolving range of SEM, PES milipore filter has been covered with the aperture of micron level, and after being coated with HTCC top layer, the aperture on film surface is visible hardly, the substitute is dense NF membrane top layer; Composition graphs 5 is known, in 10 μm × 10 μm sweep limits, the surface roughness (RMS) of PES film is 51.1nm, and the surface roughness (RMS) of composite membrane is 29.2nm, as can be seen here, the surface property of the composite nanometer filtering film of preparation comparatively before basement membrane had larger lifting.

Claims (10)

1. a Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane, is characterized in that described composite membrane is the NF membrane of positively charged, and with Quaternary Ammonium Salt of Chitosan HTCC for active layer, take poly (ether-sulfone) ultrafiltration membrane as supporting layer.
2. Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane according to claim 1, is characterized in that described composite membrane is to 1.0g/LMgCl 2the rejection of solution is 73.0%-91.9%, and the water flux of described composite membrane is 4.77-8.96Lm -2h -1, the mechanical strength of described composite membrane is 233.24-266.12MPa, and the contact angle of described composite membrane is 62.7 °-63.9 °.
3. Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane according to claim 1, is characterized in that described composite membrane is prepared by following steps:
(1) take refining HTCC sample soluble in water, be made into the casting solution of mass concentration 1.0%-2.0%;
(2) fixed on a glass by poly (ether-sulfone) ultrafiltration membrane, draw casting solution even application on film, the wet film obtained is placed in less than 50 DEG C temperature and flashes to dry film;
(3) configuration quality concentration is the epoxychloropropane ethanolic solution of 1.6%-2.2%, is placed in closed container, adds aqueous slkali;
(4) dry film in step 2 is soaked in the solution in step 3,45-55 DEG C of cross-linking reaction;
(5) after cross-linking reaction, film is taken out 45-55 DEG C of heat treatment, finally by deionized water washing, soak, to be determined.
4. Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane according to claim 3, is characterized in that the substitution value of the Quaternary Ammonium Salt of Chitosan HTCC described in step (1) is greater than 88.65%; The molecular cut off of the poly (ether-sulfone) ultrafiltration membrane described in step (2) is 10000, and effective area is 50.3cm 2.
5. Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane according to claim 3, it is characterized in that the aqueous slkali described in step (3) is the potassium hydroxide solution of 50wt%, described alkali and the amount ratio of ethanol are 4-8mg/mL; Cross-linking reaction time described in step (4) is not less than 20h; Heat treatment time described in step (5) is 20-30min.
6. a preparation method for Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane, is characterized in that comprising the following steps:
The first step, takes refining HTCC sample soluble in water, is made into the casting solution of mass concentration 1.0%-2.0%;
Second step, fixes poly (ether-sulfone) ultrafiltration membrane on a glass, and draw casting solution even application on film, the wet film obtained is placed in less than 50 DEG C temperature and flashes to dry film;
3rd step, configuration quality concentration is the epoxychloropropane ethanolic solution of 1.6%-2.2%, is placed in closed container, adds aqueous slkali;
4th step, is soaked in the solution in step 3 by the dry film in step 2,45-55 DEG C of cross-linking reaction;
5th step, after cross-linking reaction, takes out 45-55 DEG C of heat treatment by film, finally by deionized water washing, soak, to be determined.
7. the preparation method of Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane according to claim 6, is characterized in that the substitution value of the Quaternary Ammonium Salt of Chitosan HTCC described in the first step is greater than 88.65%.
8. the preparation method of Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane according to claim 6, it is characterized in that the molecular cut off of the poly (ether-sulfone) ultrafiltration membrane described in second step is 10000, effective area is 50.3cm 2.
9. the preparation method of Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane according to claim 6, it is characterized in that the aqueous slkali described in the 3rd step is the potassium hydroxide solution of 50wt%, described alkali and the amount ratio of ethanol are 4-8mg/mL.
10. the preparation method of Quaternary Ammonium Salt of Chitosan HTCC/ polyethersulfone composite membrane according to claim 6, is characterized in that the cross-linking reaction time described in the 4th step is not less than 20h; Heat treatment time described in 5th step is 20-30min.
CN201310285981.4A 2013-07-08 2013-07-08 Chitosan quaternary ammonium HTCC/polyethersulfone composite nanofiltration membrane and preparation Pending CN104275094A (en)

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CN105617890A (en) * 2016-03-18 2016-06-01 南京理工大学 Layer-by-layer self-assembly chitosan positively charged composite nanofiltration membrane and preparation method thereof
CN107081077A (en) * 2017-05-12 2017-08-22 大连理工大学 A kind of Positively charged composite nanofiltration membrane and preparation method thereof
CN107903638A (en) * 2017-11-20 2018-04-13 武汉大学 A kind of soybean protein isolate/chitosan quaternary ammonium salt composite membrane and preparation method and application
US10328386B2 (en) 2017-05-18 2019-06-25 Uop Llc Co-cast thin film composite flat sheet membranes for gas separations and olefin/paraffin separations
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US10471381B2 (en) 2016-06-09 2019-11-12 Uop Llc High selectivity facilitated transport membranes and their use for olefin/paraffin separations
US10569233B2 (en) 2017-06-06 2020-02-25 Uop Llc High permeance and high selectivity facilitated transport membranes for olefin/paraffin separations
CN110917897A (en) * 2019-12-19 2020-03-27 中化(宁波)润沃膜科技有限公司 Composite nanofiltration membrane and preparation method thereof
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CN114042383A (en) * 2021-12-16 2022-02-15 中国海洋大学 Super-hydrophilic chitosan quaternary ammonium salt hydrogel composite membrane and preparation method and application thereof

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105214523A (en) * 2015-09-21 2016-01-06 中国海洋大学 A kind of method preparing homogeneous phase hybrid organic-inorganic film
CN105617890A (en) * 2016-03-18 2016-06-01 南京理工大学 Layer-by-layer self-assembly chitosan positively charged composite nanofiltration membrane and preparation method thereof
US10471381B2 (en) 2016-06-09 2019-11-12 Uop Llc High selectivity facilitated transport membranes and their use for olefin/paraffin separations
CN107081077A (en) * 2017-05-12 2017-08-22 大连理工大学 A kind of Positively charged composite nanofiltration membrane and preparation method thereof
US10328386B2 (en) 2017-05-18 2019-06-25 Uop Llc Co-cast thin film composite flat sheet membranes for gas separations and olefin/paraffin separations
US10569233B2 (en) 2017-06-06 2020-02-25 Uop Llc High permeance and high selectivity facilitated transport membranes for olefin/paraffin separations
US10751670B2 (en) 2017-08-24 2020-08-25 Uop Llc High selectivity facilitated transport membrane comprising polyethersulfone/polyethylene oxide-polysilsesquioxane blend membrane for olefin/paraffin separations
CN107903638A (en) * 2017-11-20 2018-04-13 武汉大学 A kind of soybean protein isolate/chitosan quaternary ammonium salt composite membrane and preparation method and application
US10427997B2 (en) 2017-12-27 2019-10-01 Uop Llc Modular membrane system and method for olefin separation
CN110917897A (en) * 2019-12-19 2020-03-27 中化(宁波)润沃膜科技有限公司 Composite nanofiltration membrane and preparation method thereof
CN114042383A (en) * 2021-12-16 2022-02-15 中国海洋大学 Super-hydrophilic chitosan quaternary ammonium salt hydrogel composite membrane and preparation method and application thereof

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