CN115253729B - Sulfonated nanocellulose/sulfonated polysulfone composite membrane and preparation method and application thereof - Google Patents
Sulfonated nanocellulose/sulfonated polysulfone composite membrane and preparation method and application thereof Download PDFInfo
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- CN115253729B CN115253729B CN202210897136.1A CN202210897136A CN115253729B CN 115253729 B CN115253729 B CN 115253729B CN 202210897136 A CN202210897136 A CN 202210897136A CN 115253729 B CN115253729 B CN 115253729B
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- 239000012528 membrane Substances 0.000 title claims abstract description 132
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 84
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 6
- 229960003080 taurine Drugs 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010248 power generation Methods 0.000 abstract description 13
- 230000003204 osmotic effect Effects 0.000 abstract description 2
- 229920005597 polymer membrane Polymers 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 32
- 150000002500 ions Chemical class 0.000 description 20
- 239000002121 nanofiber Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000011780 sodium chloride Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 13
- 238000010998 test method Methods 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 7
- 238000000909 electrodialysis Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Abstract
The invention belongs to the field of polymer membranes, and particularly relates to a preparation method of a sulfonated nanocellulose/sulfonated polysulfone composite membrane and application of the sulfonated nanocellulose/sulfonated polysulfone composite membrane in ocean energy capture. The composite membrane is formed by compounding a hydrophilic sulfonated nano cellulose membrane and a hydrophobic sulfonated polysulfone membrane; adding deionized water into carboxymethyl nanocellulose, stirring in an ice water bath, performing ultrasonic stirring, and then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide to perform room temperature reaction; taurine and NaHCO 3 Adding water for dissolving, and then adding the dissolved water into the obtained product for room-temperature reaction; dialyzing the obtained product in deionized water; putting the obtained dispersion liquid into a culture dish, and drying overnight to obtain a sulfonated nanocellulose film; and dissolving the sulfonated polysulfone in a dimethyl sulfoxide solution, and centrifugally drying to obtain the sulfonated polysulfone membrane. The composite membrane can inhibit water osmotic pressure, has good ion conductivity, and can effectively improve the output power density of salt-tolerant power generation.
Description
Technical Field
The invention belongs to the field of polymer membranes, and particularly relates to a sulfonated nanocellulose/sulfonated polysulfone composite membrane, and a preparation method and application thereof.
Background
At present, energy sources in China mainly depend on fossil resources, and energy structures are required to be changed, so that the duty ratio of clean energy is improved, and energy transformation is realized. The sea area of China is wide, the river enters a plurality of seaports, and the ocean energy reserves are rich; meanwhile, the ocean energy has the advantages of being renewable, free of carbon emission, free of environmental pollution and the like.
Salt difference energy at the sea entrance of a river can be captured by adopting a reverse electrodialysis technology (RED), and sodium ions or chloride ions selectively pass through the reverse electrodialysis membrane assembly to undergo oxidation-reduction reaction on the electrode, so that the salt difference energy is converted into electric energy to be output. The reverse electrodialysis membranes currently used have the disadvantage of low energy conversion efficiency. This is mainly caused by the low ion conduction efficiency and poor ion selectivity. At present, the salt difference energy collection efficiency of the reverse electrodialysis membrane is improved mainly by reducing the membrane thickness to prepare an ultrathin membrane, improving the membrane porosity and improving the ion conductivity. However, the films prepared by the two methods have the defects of incapability of large-scale preparation and low mechanical strength. Therefore, developing a membrane with high ionic conductivity and high selectivity, which can be prepared in a large scale, has very important significance for extracting ocean energy.
The membrane modules currently involved in reverse electrodialysis technology involve selective migration of ions. Because of the existence of osmotic pressure on two sides of the membrane, water migrates from low-concentration solution to high-concentration solution, and the ion migration direction is opposite to that in the salt difference power generation process, so that the ion transmission resistance is increased, the ion conduction efficiency of the membrane is reduced, the process is often ignored in the membrane assembly design process, and the membrane can effectively improve the ion conductivity of the membrane by developing a novel membrane to inhibit the permeation of water from low concentration to high concentration.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sulfonated nanocellulose/sulfonated polysulfone composite membrane, and a preparation method and application thereof.
In order to solve the technical problems, the invention is realized as follows:
the composite membrane is formed by compositing a hydrophilic sulfonated nanocellulose membrane obtained by drying a sulfonated nanocellulose dispersion liquid and a hydrophobic sulfonated polysulfone membrane obtained by drying a sulfonated polysulfone dimethyl sulfoxide solution;
the structural formula of the sulfonated nanocellulose is as follows:
the structural formula of the sulfonated polysulfone is as follows:
x is the degree of sulfonation.
Further, the film thickness ratio of the sulfonated nano cellulose film to the sulfonated polysulfone film is 5-11: 12-6.
Further, the sulfonation degree of the sulfonated polysulfone is more than or equal to 40% and less than or equal to 80%.
The preparation method of the sulfonated nanocellulose/sulfonated polysulfone composite membrane comprises the step of compositing a hydrophilic sulfonated nanocellulose membrane and a hydrophobic sulfonated polysulfone membrane;
the preparation method of the sulfonated nanocellulose film comprises the following steps:
a 1 adding deionized water into carboxymethyl nanocellulose, stirring in an ice water bath, performing ultrasonic stirring, and then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide to perform room temperature reaction;
b 1 taurine and NaHCO 3 Adding water for dissolving, and then adding the solution into the step a 1 Carrying out room temperature reaction in the obtained product;
c 1 step b 1 Dialyzing the obtained product in deionized water to obtain sulfonated nanocellulose dispersion;
d 1 step c 1 Placing the obtained sulfonated nanocellulose dispersion liquid into a culture dish, and drying overnight to obtain the sulfonated nanocellulose membrane;
the preparation method of the sulfonated polysulfone membrane comprises the following steps: and dissolving the sulfonated polysulfone in a dimethyl sulfoxide solution, and centrifugally drying to obtain the sulfonated polysulfone membrane.
The structural formulas of the sulfonated nanocellulose and the sulfonated polysulfone are as follows:
x is the degree of sulfonation
Further, step a of the present invention 1 Wherein the concentration of the carboxymethyl nanocellulose is 1.0wt%, the carboxyl content is 0.5mmol, the stirring time of the ice water bath is 1 hour, the ultrasonic stirring time is 30 minutes, and the reaction time at room temperature is 30 minutes; said step b 1 The reaction time at room temperature was 20 hours.
Further, step d of the present invention 1 The concentration of the sulfonated nanocellulose dispersion was 0.2wt%.
Further, the invention dissolves sulfonated polysulfone in dimethyl sulfoxide solution to prepare 2wt% solution, and the solution is centrifuged for 12000 turns to remove undissolved substances, and the solution is dried overnight in an 80-DEG oven to obtain the sulfonated polysulfone membrane.
The product obtained by the preparation method of the sulfonated nanocellulose/sulfonated polysulfone composite membrane is applied to ocean energy capture.
The output power density of the sulfonated nanocellulose/sulfonated polysulfone (40-80% sulfonation degree) composite membrane is greater than or equal to 4.3W/M under the conditions of artificial seawater (0.5M NaCl) and fresh water (0.01M NaCl) in the salt difference power generation 2 。
Compared with the prior art, the sulfonated nanocellulose/sulfonated polysulfone composite membrane disclosed by the invention has higher output power density in ocean energy capture. The wettability of two sides of the sulfonated nanocellulose/sulfonated polysulfone composite membrane is different, water automatically migrates from the hydrophobic side (the sulfonated polysulfone side) of the composite membrane to the hydrophilic side (the sulfonated nanofiber side) of the composite membrane, and when the migration direction is the same as the ion migration direction, the ion conduction efficiency is effectively improved, and the ocean energy capturing efficiency is improved. Compared with the traditional ocean energy capture membrane, the membrane has good application prospect. According to the invention, the nano sulfonated nanocellulose with different sulfonation degrees is prepared by changing the dosage of an activating reagent 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, N-hydroxysuccinimide and a reactant taurine in a system, so that an effective active site is provided for ion directional transmission. The membrane material is divided into a conductive region and a non-conductive region, wherein the conductive region is an ion transmission channel region formed by interaction of sulfonic acid groups, and the non-conductive region is a polymer supporting region. The higher the ionization degree of the membrane material is, the higher the ionic conductivity is, the sulfonated nano cellulose membrane grafted and modified by the sulfonic group can promote the adsorption and ionic conduction of the membrane to water molecules, and effectively improve the ion transmission flux of the membrane, but the sulfonation degree of the membrane improves the swelling degree of the membrane, reduces the stability and the ionic selectivity of the membrane, and further reduces the salt difference power generation performance of the membrane. According to the invention, the self-assembly process of the nanocellulose is regulated, so that the space between nanofibers is effectively controlled, the ion mass transfer behavior is not limited by the influence of an ion exchange mechanism and electrostatic repulsion factors, and the steric hindrance is utilized to generate a screening effect, so that the ion diffusion selectivity is formed. The polysulfone material has the characteristics of high mechanical strength, compression tightness, chemical stability, heat resistance and the like, but the hydrophobic solute is very easy to cause adsorption and deposition on the surface of the membrane, so that the membrane pores are blocked, the membrane performance is reduced, and the properties of the polysulfone membrane can be obviously improved after the polysulfone material is subjected to sulfonation modification. In addition, as the sulfonation degree of the sulfonated polysulfone is increased, the IEC value of the membrane is increased, the resistance is reduced, the mass transfer capacity of the ion exchange membrane is enhanced, but the selectivity of the membrane is reduced due to the swelling of the membrane (the IEC value is increased, the swelling of the membrane is enhanced, and the pore diameter is enlarged), and the ion selectivity of the membrane is improved due to the difference of the sulfonation degree and the space of two layers after the composite membrane is formed. Meanwhile, the wettability of the membrane is changed, the wettability difference of the two sides of the membrane is changed after the sulfonated nanocellulose is formed into a composite membrane, and the water transmission performance and the ion transmission performance are changed along with the wettability difference, so that the salt difference power density is affected. Secondly, the inventor researches and discovers that the thickness ratio of the sulfonated nanocellulose membrane layer to the sulfonated polysulfone composite membrane layer in the composite membrane is an important factor influencing the membrane resistance and the membrane power generation power density, and ions have larger difference in ion conductivity and ion selectivity in the composite membranes with the same thickness but different thickness ratios. The film thickness ratio adopted by the scheme can achieve ideal coordination effect on the chemical stability, mechanical strength and film power generation power density index of the composite film.
Drawings
The invention is further described below with reference to the drawings and the detailed description. The scope of the present invention is not limited to the following description.
FIG. 1 is a photograph of a sulfonated nanocellulose surface electron microscope;
FIG. 2 is a section electron microscope image of sulfonated nanocellulose;
FIG. 3 is an infrared spectrum of sulfonated nanofiber membranes and nanocellulose membranes;
FIG. 4 is a Transmission Electron Microscope (TEM) image of 40% sulfonated polysulfone;
fig. 5 is a schematic diagram of a salt-tolerant power generator.
Detailed Description
Example 1
50g (carboxyl content 0.5 mmol) of Carboxymethyl Nanocellulose (CNF) with the weight percent is taken, 200ml of deionized water is added, the solution is vigorously stirred for 1 hour in an ice water bath, ultrasonic treatment is carried out for 30 minutes, the solution is repeated three times, 0.58g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide (EDC. HCl) and 0.53g (7.5 mmol) of N-hydroxysuccinimide (NHS) are added into a reaction system, the reaction is carried out for 30 minutes at room temperature, and 0.75g of taurine and 0.5g of NaHCO are reacted 3 Adding water for dissolution, adding the reaction system, and reacting for 20 hours at room temperature. And dialyzing the reacted dispersion liquid in deionized water to obtain the sulfonated nanocellulose dispersion liquid.
The preparation method of the sulfonated nanocellulose film comprises the following specific steps:
taking 5ml0.2wt% dispersion was placed in a 6cm diameter petri dish and dried overnight to give a sulfonated nanocellulose film (FIGS. 1, 2). The film thickness was found to be 8 μm. To verify whether nanocellulose was successfully modified, fourier infrared spectroscopy tests were performed on the nanocellulose films prepared (fig. 3). As can be seen from FIG. 3, at 1647cm -1 A new peak appears at the position, which is the stretching vibration peak of the amide bond; at the same time at 1216cm -1 A new peak appears at the position, which is an expansion vibration peak of S-O, and shows that the sulfonic acid group is successfully grafted to the nanocellulose, and the modification is successful.
The preparation method of the sulfonated polysulfone membrane comprises the following steps: the sulfonated polysulfone with 40% sulfonation degree was dissolved in dimethyl sulfoxide solution to prepare 2wt% solution, and undissolved substances were removed by centrifugation at 12000 rpm, 2ml was placed in a glass petri dish, and dried overnight in an 80-degree oven to obtain a sulfonated polysulfone membrane (FIG. 4). The film thickness was measured to be 9. Mu.m.
Preparation of sulfonated nanocellulose/sulfonated polysulfone composite membrane: and the sulfonated polysulfone membrane is covered above the water-absorbing sulfonated nano cellulose membrane, so that the tightly-adhered composite membrane is obtained.
Salt difference power generation performance test:
a schematic diagram of a salt difference power generation device used for the salt difference power generation test is shown in fig. 5. Electrolyte solutions of different concentrations are filled into two empty chambers on both sides of the membrane. Ag/AgCl electrodes are added on two sides of the membrane, and a load resistor is externally connected. The test mode is current scanning, the resistance value of a load resistor is regulated, the current value read by an instrument is recorded, and the current value can be read according to P=I 2 ×R L (P is output power density, I is current, R L The power generation power is calculated for the external resistor, under the conditions of artificial seawater (0.5M NaCl) and fresh water (0.01M NaCl), when the seawater is on one side of the sulfonated polysulfone membrane, the output power density is 8.3W/M 2 。
Example 2 (comparative example)
The preparation method of the sulfonated nanofiber membrane is described in example 1. 11.2ml of the 0.2% by weight dispersion was placed in a 34mm diameter petri dish and dried overnight with a film thickness of 17. Mu.m. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 3.7W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 3 (comparative example)
The preparation method of the sulfonated polysulfone membrane is described in example 1. 3.8ml of a 2wt% solution was placed in a 6cm diameter petri dish and dried overnight with a film thickness of 17. Mu.m. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 5.6W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 4
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The test of the performance of the salt difference power generation film, in which the thickness of the sulfonated nanofiber layer is 5 μm and the thickness of the sulfonated polysulfone layer is 12 μm, was conducted by the same method as that of the used device in example 1. The power density of the membrane reaches 5.6W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 5
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The test of the performance of the salt difference power generation film, in which the thickness of the sulfonated nanofiber layer is 11 μm and the thickness of the sulfonated polysulfone layer is 6 μm, was conducted by the same method as that of the used device in example 1. The power density of the membrane reaches 7.9W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 6
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The test of the performance of the salt difference power generation film, in which the thickness of the sulfonated nanofiber layer is 13 μm and the thickness of the sulfonated polysulfone layer is 4 μm, was conducted by the same method as that of the used device in example 1. The power density of the membrane reaches 6.8W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 7
50g (carboxyl content 0.5 mmol) of Carboxymethyl Nanocellulose (CNF) with the weight percent is taken, 200ml of deionized water is added, the solution is vigorously stirred for 1 hour in an ice water bath, ultrasonic treatment is carried out for 30 minutes, the solution is repeated three times, 0.29g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide (EDC. HCl) and 0.26g (7.5 mmol) of N-hydroxysuccinimide (NHS) are added into a reaction system, the reaction is carried out for 30 minutes at room temperature, and 0.25g of taurine and 0.2 g of NaHCO are reacted 3 Adding water for dissolution, adding the reaction system, and reacting for 20 hours at room temperature. Dispersion after reactionDialyzing the solution in deionized water to obtain sulfonated nanocellulose dispersion. The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 40%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 6.0W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 8
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 60%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 7.2W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 9
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 70%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 6.5W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 10
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 80%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 4.3W/M under the gradient of 0.01M/0.5M NaCl 2 。
Example 11
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 40%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 8.2W/M under the condition of 0.01M/0.5M NaCl gradient and pH value of 3 2 。
Example 12
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 40%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The membrane power densityUnder the condition of 0.01M/0.5M NaCl gradient, the pH value is 9 and reaches 8.2W/M 2 。
Example 13
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 40%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 19.6W/M under the gradient of 0.01M/5M NaCl 2 。
Example 14
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 40%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 10.6W/M under the gradient of 0.01M/0.5M KCl 2 。
Example 15
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 40%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane reaches 5.3W/M under the gradient of 0.01M/0.5M LiCl 2 。
Example 16
The preparation method of the sulfonated nanofiber/sulfonated polysulfone composite membrane is described in example 1. The sulfonated polysulfone layer had a degree of sulfonation of 40%. Test of the performance of the salt-differential power generating film the test method and the device used refer to example 1. The power density of the membrane is 0.01M/0.5M CaCl 2 The gradient reaches 5.3W/m 2 。
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, if and when such modifications and variations of the present invention fall within the scope of the claims and the equivalents thereof, the present invention is intended to encompass such modifications and variations.
The above list of preferred embodiments of the present invention is, of course, not intended to limit the scope of the invention, and equivalent variations according to the claims of the present invention are therefore included in the scope of the present invention.
Claims (5)
1. The preparation method of the sulfonated nanocellulose/sulfonated polysulfone composite membrane is characterized by comprising the following steps of: the preparation method of the sulfonated nanocellulose film comprises the following steps:
a 1 adding deionized water into carboxymethyl nanocellulose, stirring in an ice water bath, performing ultrasonic stirring, and then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and N-hydroxysuccinimide to perform room temperature reaction;
b 1 taurine and NaHCO 3 Adding water for dissolving, and then adding the solution into the step a 1 Carrying out room temperature reaction in the obtained product;
c 1 step b 1 Dialyzing the obtained product in deionized water to obtain sulfonated nanocellulose dispersion;
d 1 step c 1 Placing the obtained sulfonated nanocellulose dispersion liquid into a culture dish, and drying overnight to obtain the sulfonated nanocellulose membrane;
the preparation method of the sulfonated polysulfone membrane comprises the following steps: dissolving sulfonated polysulfone in dimethyl sulfoxide solution, and centrifugally drying to obtain a sulfonated polysulfone membrane; preparation of sulfonated nanocellulose/sulfonated polysulfone composite membrane: the sulfonated polysulfone membrane is covered above the water-absorbing sulfonated nano cellulose membrane, so that a tightly-adhered composite membrane is obtained;
the sulfonated nano cellulose/sulfonated polysulfone composite membrane is formed by compounding a hydrophilic sulfonated nano cellulose membrane obtained by drying a sulfonated nano cellulose dispersion liquid and a hydrophobic sulfonated polysulfone membrane obtained by drying a sulfonated polysulfone dimethyl sulfoxide solution;
the structural formula of the sulfonated nanocellulose is as follows:
the structural formula of the sulfonated polysulfone is as follows:
x is the degree of sulfonation;
the membrane thickness ratio of the sulfonated nano cellulose membrane to the sulfonated polysulfone membrane is 5-11: 12-6; the sulfonation degree of the sulfonated polysulfone is more than or equal to 40% and less than or equal to 80%.
2. The method for preparing the sulfonated nanocellulose/sulfonated polysulfone composite membrane according to claim 1, wherein: said step a 1 Wherein the concentration of the carboxymethyl nanocellulose is 1.0wt%, the carboxyl content is 0.5mmol, the stirring time of the ice water bath is 1 hour, the ultrasonic stirring time is 30 minutes, and the reaction time at room temperature is 30 minutes; said step b 1 The reaction time at room temperature was 20 hours.
3. The method for preparing the sulfonated nanocellulose/sulfonated polysulfone composite membrane according to claim 2, wherein: said step d 1 The concentration of the sulfonated nanocellulose dispersion was 0.2wt%.
4. The method for preparing the sulfonated nanocellulose/sulfonated polysulfone composite membrane as claimed in claim 3, wherein: dissolving sulfonated polysulfone in dimethyl sulfoxide solution, preparing 2wt% solution, centrifuging for 12000 r to remove undissolved substances, and drying overnight in an 80 ℃ oven to obtain the sulfonated polysulfone membrane.
5. The use of a composite membrane obtained by the method for preparing a sulfonated nanocellulose/sulfonated polysulfone composite membrane according to any one of claims 1 to 4 in ocean energy capture.
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