CN111437740B - Preparation method of sodium lignosulfonate-based high-flux high-interception nanofiltration membrane - Google Patents
Preparation method of sodium lignosulfonate-based high-flux high-interception nanofiltration membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 159
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 59
- 229920005552 sodium lignosulfonate Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 71
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 29
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims abstract description 14
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229920001131 Pulp (paper) Polymers 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 23
- 230000004907 flux Effects 0.000 description 18
- 239000002131 composite material Substances 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- -1 sulfonic group Chemical group 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- B01D71/74—Natural macromolecular material or derivatives thereof
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
Abstract
A preparation method of a sodium lignosulphonate-based high-flux high-interception nanofiltration membrane belongs to the field of material preparation. The method comprises the following steps: preparing aqueous solution of sodium lignosulfonate and triethylamine; preparing a 1,3, 5-trimesoyl chloride n-hexane solution; pouring the prepared water solution onto the surface of the polysulfone basal membrane; taking out the polysulfone base membrane after 1-15 minutes, and standing in the air for 2-10 minutes to remove excessive moisture; pouring the prepared n-hexane solution onto the surface of the membrane and immersing for 1-20 minutes; taking out the film, and placing the film in the air for 2-10 minutes; and (3) carrying out heat treatment on the film in an oven at the temperature of 40-100 ℃ for 5-20 minutes, then taking out the film, and soaking the film in water. The method adopts an interfacial polymerization method to use the sodium lignin sulfonate for preparing the nanofiltration membrane, has simple process and convenient preparation, enables the sodium lignin sulfonate in the paper pulp waste liquid to be efficiently utilized, and provides possibility for large-scale application of the nanofiltration membrane. The invention is applied to the field of nanofiltration membranes.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a preparation method of a sodium lignosulphonate-based high-flux high-interception nanofiltration membrane.
Background
Membrane separation techniques are widely studied and applied due to their precise separation effect, low energy consumption, high efficiency, etc. Nanofiltration membranes are used in many fields due to the separation of nanoscale substances. The nanofiltration membrane can be prepared by an interfacial polymerization method. The sodium lignosulfonate is a natural high polymer, is a main component of sulfite pulp waste liquor, has high yield and low price, contains abundant functional groups such as phenolic hydroxyl, alcoholic hydroxyl, sulfonic group, carboxyl and the like in a molecular structure, and has better hydrophilicity and reactivity. Therefore, the utilization rate of the sodium lignosulfonate is improved, and the sodium lignosulfonate has potential significance in preparing the nanofiltration membrane with high application value.
CN109364759A, invention name: a calcium lignosulfonate solvent-resistant composite nanofiltration membrane and a preparation method thereof are disclosed, and the prepared calcium lignosulfonate solvent-resistant composite nanofiltration membrane has the advantages of high flux, good solvent resistance, low raw material cost, simple process and the like. However, the flux of the nanofiltration membrane prepared by the patent is increased to some extent by adding the pore-forming agent, but the interception of the membrane is not reduced enough, and the interception performance of the membrane cannot be maintained while the flux of the membrane is improved. CN106268374B, invention name: a composite lignin nanofiltration membrane and its preparing process are disclosed, which features cheap and easily available raw materials, simple process and quick reaction. The obtained lignin composite nanofiltration membrane has the advantages of higher flux and higher separation selectivity. But the flux and separation selectivity are still low compared to the present invention.
CN107261871A, invention name: a preparation method of a polyethyleneimine/sodium lignosulfonate composite membrane; and CN108325390A, entitled: a method for improving the performance of a polyethyleneimine/sodium lignosulfonate composite membrane; the composite membrane is prepared by using a polysulfone ultrafiltration membrane with a negatively charged surface as a base membrane, sequentially self-assembling polyethyleneimine and sodium lignosulfonate on the base membrane to form a self-assembled composite layer, and then crosslinking through glutaraldehyde to form a composite layer with a stable structure. The advantage of the patent is that the anion and cation polyelectrolyte can be adsorbed on the surface of the polysulfone ultrafiltration membrane layer by utilizing the electrostatic interaction between electrolytes with different charges, thereby realizing the layer-by-layer self-assembly of the polyelectrolyte. When the number of the polyelectrolyte double-layer is 7, the composite nanofiltration membrane shows better separation performance.
However, compared with the present invention, the preparation process is complex and time-consuming, and the flux of the membrane cannot be effectively improved on the premise of maintaining the separation selectivity of the membrane.
CN109464918A, invention name: a high-performance hydrophilic composite nano-filter membrane is prepared through carrying a monomer with negative charge on the surface of ultra-filter membrane, adding a monomer with positive charge, and repeating said steps. The prepared nanofiltration membrane has excellent separation performance on double high-valence ions and can be used for salt solution (such as MgSO (MgSO)) containing high-valence cations or high-valence anions4、MgCl2、Na2SO4Etc.) have high retention rates and permeate fluxes. The invention has the characteristics of easy implementation, controllable reaction, adjustable separation performance of the membrane in a larger range and the like. But the preparation process is complicated and time-consuming compared to the present invention, and the flux and separation selectivity of the membrane are low.
Disclosure of Invention
The invention aims to improve the utilization rate of sodium lignosulfonate, and provides a preparation method of a sodium lignosulfonate-based high-flux high-interception nanofiltration membrane for synchronously improving the permeation flux and the interception rate of the prepared nanofiltration membrane by improving a membrane preparation process.
The invention relates to a preparation method of a sodium lignosulfonate-based high-flux high-interception nanofiltration membrane, which comprises the following specific steps:
the method comprises the following steps: preparing 0.1-15% by mass of sodium lignosulfonate and 0.1-3% by mass of triethylamine aqueous solution;
step two: preparing a 1,3, 5-trimesoyl chloride n-hexane solution with the mass fraction of 0.05-0.3%;
step three: pouring the sodium lignosulfonate aqueous solution prepared in the step one into the surface of the polysulfone base membrane, and immersing the polysulfone membrane for 1-15 minutes;
step four: removing the sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane in the step three, and placing the polysulfone membrane in the air for 2-10 minutes to remove the redundant sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane;
step five: pouring the 1,3, 5-trimesoyl chloride normal hexane solution prepared in the second step into the surface of the polysulfone membrane obtained in the fourth step, and immersing the polysulfone membrane for 1-20 minutes;
step six: removing the 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane in the step five, and standing in the air for 2-10 minutes to remove the redundant 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane;
step seven: carrying out heat treatment on the polysulfone membrane prepared in the step six in an oven at the temperature of 40-100 ℃ for 5-20 minutes, taking out, and soaking in water for 24 hours, and changing water for many times; obtaining the sodium lignosulfonate-based nanofiltration membrane prepared based on the interfacial polymerization method;
step eight: and (4) placing the nanofiltration membrane prepared in the step seven in water at 4 ℃ for storage and later use.
The invention is based on an interfacial polymerization method, sodium lignosulfonate aqueous solution containing functional groups such as abundant phenolic hydroxyl, alcoholic hydroxyl, sulfonic group, carboxyl and the like is taken as a water phase, and is subjected to interfacial polymerization with n-hexane solution of 1,3, 5-trimesoyl chloride, triethylamine is added into the water phase, so that the reaction activity of the interfacial polymerization is increased, a nanofiltration separation layer which is uniformly distributed is obtained, and the sodium lignosulfonate has better hydrophilic performance, so that the prepared nanofiltration membrane has good interception performance and high permeation flux, and the interception rate of the prepared nanofiltration membrane to sunset yellow can reach 99.02 percentWhile the permeation flux of the membrane is up to 14.03Lm-2·h-1·bar-1. The nanofiltration membrane prepared by the interfacial polymerization method can fully utilize sodium lignin sulfonate in the pulp waste liquid, and the prepared nanofiltration membrane has an excellent separation effect, so that the possibility of using the nanofiltration membrane in more fields is provided.
Drawings
FIG. 1 is a scanning electron micrograph of the polysulfone-based film surface;
FIG. 2 is a scanning electron microscope image of the surface of the nanofiltration membrane prepared in example 1;
FIG. 3 is a graph showing UV absorption spectrum measurements of a filtrate after membrane separation and preparation of sunset yellow dye in example 1;
FIG. 4 is a scanning electron micrograph of the surface of the nanofiltration membrane prepared in example 2;
FIG. 5 is a graph showing UV absorption spectrum measurements of the filtrate after membrane separation and the sunset yellow dye formulated in example 2.
FIG. 6 is a scanning electron micrograph of the surface of the nanofiltration membrane prepared in example 3;
FIG. 7 is a graph showing UV absorption spectrum measurements of the filtrate after membrane separation and the formulated sunset yellow dye of example 3.
Detailed Description
The first embodiment is as follows: the embodiment of the invention provides a preparation method of a sodium lignosulfonate-based high-flux high-interception nanofiltration membrane, which comprises the following specific steps:
the method comprises the following steps: preparing 0.1-15% by mass of sodium lignosulfonate and 0.1-3% by mass of triethylamine aqueous solution;
step two: preparing a 1,3, 5-trimesoyl chloride n-hexane solution with the mass fraction of 0.05-0.3%;
step three: pouring the sodium lignosulfonate aqueous solution prepared in the step one into the surface of the polysulfone base membrane, and immersing the polysulfone membrane for 1-15 minutes;
step four: removing the sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane in the third step, and placing the polysulfone membrane in the air for 2-10 minutes to remove the redundant sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane;
step five: pouring the 1,3, 5-trimesoyl chloride normal hexane solution prepared in the second step into the surface of the polysulfone membrane obtained in the fourth step, and immersing the polysulfone membrane for 1-20 minutes;
step six: removing the 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane in the fifth step, and standing in the air for 2-10 minutes to remove the redundant 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane;
step seven: carrying out heat treatment on the polysulfone membrane prepared in the step six in an oven at the temperature of 40-100 ℃ for 5-20 minutes, taking out, and soaking in water for 24 hours, and changing water for many times; obtaining the sodium lignosulfonate-based nanofiltration membrane prepared based on the interfacial polymerization method;
step eight: and (4) placing the nanofiltration membrane prepared in the step seven in water at 4 ℃ for storage and later use.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the mass fraction of the sodium lignosulfonate is 1-10%. The rest is the same as the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: and in the third step, the immersion time is 2-10 minutes. The rest is the same as the first embodiment.
The fourth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: and in the fifth step, the immersion time is 2-15 minutes. The rest is the same as the first embodiment.
The fifth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: and seventhly, the heat treatment temperature is 50-90 ℃. The rest is the same as the first embodiment.
The sixth specific implementation mode: the first difference between the present embodiment and the specific embodiment is: and the treatment time in the seventh step is 10-20 minutes. The rest is the same as the first embodiment.
The seventh embodiment: the first difference between the present embodiment and the specific embodiment is: the mass fraction of triethylamine is 0.5-2.5%. The rest is the same as the first embodiment.
The specific implementation mode is eight: the first difference between the present embodiment and the specific embodiment is: the mass fraction of triethylamine is 1-2%. The rest is the same as the first embodiment.
The specific implementation method nine: the first difference between the present embodiment and the specific embodiment is: the mass fraction of triethylamine is 1.5-2%. The rest is the same as the first embodiment.
The detailed implementation mode is ten: the first difference between the present embodiment and the specific embodiment is: the mass fraction of triethylamine is 1-2.5%. The rest is the same as the first embodiment.
The beneficial effects of the present invention are demonstrated by the following examples:
example 1
The preparation method of the sodium lignosulfonate-based high-flux high-interception nanofiltration membrane comprises the following specific steps:
the method comprises the following steps: preparing sodium lignosulfonate with the mass fraction of 5% and triethylamine aqueous solution with the mass fraction of 1%;
step two: preparing a 1,3, 5-trimesoyl chloride n-hexane solution with the mass fraction of 0.2%;
step three: pouring the sodium lignosulfonate aqueous solution prepared in the step one into the surface of the polysulfone base membrane, and immersing for 3-6 minutes;
step four: removing the sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane in the step three, and placing the polysulfone membrane in the air for 2-5 minutes to remove the redundant sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane;
step five: pouring the 1,3, 5-trimesoyl chloride normal hexane solution prepared in the second step into the surface of the polysulfone membrane obtained in the fourth step, and immersing for 2-12 minutes;
step six: removing the 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane in the step five, and standing in the air for 3-8 minutes to remove the redundant 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane;
step seven: carrying out heat treatment on the polysulfone membrane prepared in the step six in an oven at the temperature of 60-90 ℃ for 10-15 minutes, taking out the polysulfone membrane, and soaking the polysulfone membrane in water for 24 hours for changing water for many times;
step eight: placing the polysulfone membrane prepared in the step seven in water at 4 ℃ for storage for later use;
step nine: and (3) performing a Scanning Electron Microscope (SEM) test on the nanofiltration membrane prepared in the step eight as shown in figure 2, and comparing the nanofiltration membrane with a polysulfone-based membrane as shown in figure 1 to find that the surface of the membrane is uniformly covered with a separation layer. 100ppm of sunset yellow (molecular weight: 452.38) dye in water was prepared, and the prepared membrane was tested for flux and retention under 5bar pressure and had a flux of 14.63Lm-2·h-1·bar-1On the other hand, the retention test for sunset yellow is shown in fig. 3, wherein the ultraviolet absorption spectrum of the feed solution is the test result after twice dilution, and it can be seen from the figure that the extremely low retention rate of the dye content in the separation filtrate of the prepared membrane can reach about 98.80%.
Example 2
A preparation method of a sodium lignosulphonate-based high-flux high-interception nanofiltration membrane comprises the following specific steps:
the method comprises the following steps: preparing sodium lignosulfonate with the mass fraction of 3% and triethylamine aqueous solution with the mass fraction of 1%;
step two: preparing a 1,3, 5-trimesoyl chloride n-hexane solution with the mass fraction of 0.2%;
step three: pouring the sodium lignosulfonate aqueous solution prepared in the step one into the surface of the polysulfone base membrane, and immersing for 3-6 minutes;
step four: removing the sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane in the step three, and placing the polysulfone membrane in the air for 2-5 minutes to remove the redundant sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane;
step five: pouring the 1,3, 5-trimesoyl chloride normal hexane solution prepared in the second step into the surface of the polysulfone membrane obtained in the fourth step, and immersing for 2-12 minutes;
step six: removing the 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane in the step five, and standing in the air for 3-8 minutes to remove the redundant 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane;
step seven: carrying out heat treatment on the polysulfone membrane prepared in the step six in an oven at the temperature of 60-90 ℃ for 10-15 minutes, taking out the polysulfone membrane, and soaking the polysulfone membrane in water for 24 hours for changing water for many times;
step eight: placing the polysulfone membrane prepared in the step seven in water at 4 ℃ for storage for later use;
step nine: and (3) performing a Scanning Electron Microscope (SEM) test on the nanofiltration membrane prepared in the step eight as shown in figure 4, and comparing the nanofiltration membrane with a polysulfone-based membrane as shown in figure 1 to find that the surface of the membrane is uniformly covered with a separation layer. 100ppm of sunset yellow (molecular weight: 452.38) dye aqueous solution is prepared, and flux and interception tests are carried out on the prepared membrane under the condition of 5bar pressure, wherein the flux of the prepared membrane is 14.03Lm-2·h-1·bar-1On the other hand, the retention test for sunset yellow is shown in fig. 5, wherein the ultraviolet absorption spectrum of the feed solution is the test result after twice dilution, and it can be seen from the figure that the extremely low retention rate of the dye content in the separation filtrate of the prepared membrane can reach about 99.02%.
Example 3
A preparation method of a sodium lignosulphonate-based high-flux high-interception nanofiltration membrane comprises the following specific steps:
the method comprises the following steps: preparing sodium lignosulfonate with the mass fraction of 2% and triethylamine aqueous solution with the mass fraction of 1%;
step two: preparing a 1,3, 5-trimesoyl chloride n-hexane solution with the mass fraction of 0.2%;
step three: pouring the sodium lignosulfonate aqueous solution prepared in the step one into the surface of the polysulfone base membrane, and immersing for 3-6 minutes;
step four: removing the sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane in the step three, and placing the polysulfone membrane in the air for 2-5 minutes to remove the redundant sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane;
step five: pouring the 1,3, 5-trimesoyl chloride normal hexane solution prepared in the second step into the surface of the polysulfone membrane obtained in the fourth step, and immersing for 2-12 minutes;
step six: removing the 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane in the step five, and standing in the air for 3-8 minutes to remove the redundant 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane;
step seven: carrying out heat treatment on the polysulfone membrane prepared in the step six in an oven at the temperature of 60-90 ℃ for 10-15 minutes, taking out the polysulfone membrane, and soaking the polysulfone membrane in water for 24 hours for changing water for many times;
step eight: placing the polysulfone membrane prepared in the step seven in water at 4 ℃ for storage for later use;
step nine: scanning Electron Microscope (SEM) tests are carried out on the nanofiltration membrane prepared in the step eight as shown in figure 6, and comparison with a polysulfone-based membrane as shown in figure 1 shows that the surface of the membrane is uniformly covered with a separation layer. 100ppm of sunset yellow (molecular weight: 452.38) dye aqueous solution is prepared, and flux and interception tests are carried out on the prepared membrane under the condition of 5bar pressure, wherein the flux of the prepared membrane is 15.16Lm-2·h-1·bar-1On the other hand, the retention test for sunset yellow is shown in fig. 7, wherein the ultraviolet absorption spectrum of the feed solution is the test result after dilution by two times, and it can be seen from the figure that the extremely low retention rate of the dye content in the separation filtrate of the prepared membrane can reach about 97.69%.
The embodiment is based on an interfacial polymerization method, sodium lignosulfonate aqueous solution containing rich functional groups such as phenolic hydroxyl, alcoholic hydroxyl, sulfonic group and carboxyl is taken as a water phase, interfacial polymerization is carried out with n-hexane solution of 1,3, 5-trimesoyl chloride, triethylamine is added into the water phase, so that the reaction activity of the interfacial polymerization is increased, a uniformly distributed nanofiltration separation layer is obtained, and the sodium lignosulfonate has good hydrophilic performance, so that the prepared nanofiltration membrane has good interception performance and high permeation flux. The nanofiltration membrane prepared by the interfacial polymerization method can fully utilize sodium lignin sulfonate in the pulp waste liquid, and the prepared nanofiltration membrane has an excellent separation effect, so that the possibility of using the nanofiltration membrane in more fields is provided.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.
The present invention is not limited to the above description of the embodiments, and those skilled in the art should, in light of the present disclosure, appreciate that many changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a sodium lignosulfonate-based high-flux high-interception nanofiltration membrane is characterized by comprising the following specific steps:
the method comprises the following steps: preparing 0.1-15% by mass of sodium lignosulfonate and 0.1-3% by mass of triethylamine aqueous solution;
step two: preparing a 1,3, 5-trimesoyl chloride n-hexane solution with the mass fraction of 0.05-0.3%;
step three: pouring the sodium lignosulfonate aqueous solution prepared in the step one onto the surface of the polysulfone base membrane, and immersing the polysulfone membrane for 1-15 minutes;
step four: removing the sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane in the step three, and placing the polysulfone membrane in the air for 2-10 minutes to remove the redundant sodium lignosulfonate aqueous solution on the surface of the polysulfone membrane;
step five: pouring the 1,3, 5-trimesoyl chloride normal hexane solution prepared in the second step into the surface of the polysulfone membrane obtained in the fourth step, wherein the immersion time of the polysulfone membrane is 1-20 minutes;
step six: removing the 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane in the step five, and standing in the air for 2-10 minutes to remove the redundant 1,3, 5-trimesoyl chloride n-hexane solution on the surface of the polysulfone membrane;
step seven: carrying out heat treatment on the polysulfone membrane prepared in the step six in an oven at the temperature of 40-100 ℃ for 5-20 minutes, taking out, and soaking in water for 24 hours, and changing water for many times; obtaining the sodium lignosulfonate-based nanofiltration membrane prepared based on the interfacial polymerization method;
step eight: and (4) placing the nanofiltration membrane prepared in the step seven in water at 4 ℃ for storage and later use.
2. The method for preparing the high-flux high-rejection nanofiltration membrane based on the sodium lignin sulfonate as claimed in claim 1, wherein the mass fraction of the sodium lignin sulfonate in the step one is 1-10%.
3. The method for preparing the sodium lignin sulfonate-based high-flux high-rejection nanofiltration membrane according to claim 1, wherein the immersion time in the third step is 2-10 minutes.
4. The method for preparing the sodium lignin sulfonate-based high-flux high-rejection nanofiltration membrane according to claim 1, wherein the immersion time in the fifth step is 2-15 minutes.
5. The method for preparing the sodium lignin sulfonate-based high-flux high-rejection nanofiltration membrane according to claim 1, wherein the heat treatment temperature in the seventh step is 50-90 ℃.
6. The preparation method of the sodium lignin sulfonate-based high-flux high-rejection nanofiltration membrane according to claim 1, wherein the treatment time in the seventh step is 10-20 minutes.
7. The method for preparing the sodium lignin sulfonate-based high-flux high-rejection nanofiltration membrane according to claim 1, wherein the triethylamine accounts for 0.5-2.5% by mass.
8. The method for preparing the sodium lignin sulfonate-based high-flux high-rejection nanofiltration membrane according to claim 1 or 7, wherein the mass fraction of triethylamine is 1-2%.
9. The method for preparing a sodium lignin sulfonate-based high-flux high-rejection nanofiltration membrane according to claim 1, wherein the mass fraction of triethylamine is 1.5-2%.
10. The method for preparing the sodium lignin sulfonate-based high-flux high-rejection nanofiltration membrane according to claim 1, wherein the triethylamine accounts for 1-2.5% by mass.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1356856A1 (en) * | 2002-04-17 | 2003-10-29 | Korea Research Institute Of Chemical Technology | Silicone-coated organic solvent resistant polyamide composite nanofiltration membrane, and method for preparing the same |
| CN103816817A (en) * | 2014-01-28 | 2014-05-28 | 中国科学院化学研究所 | Alkali-resistant cellulose membrane and preparation method thereof |
| CN104759214A (en) * | 2015-03-27 | 2015-07-08 | 北京工业大学 | Preparation method of superhydrophilic/superhydrophobic composite nanofiltration membrane |
| CN105056777A (en) * | 2015-07-16 | 2015-11-18 | 宁波大学 | Lignin-crosslinking modified polymer separation membrane and application thereof |
| CN107261871A (en) * | 2017-08-08 | 2017-10-20 | 北京林业大学 | A kind of preparation method of polyethyleneimine/sodium lignin sulfonate composite membrane |
| CN107899434A (en) * | 2017-09-25 | 2018-04-13 | 浙江理工大学 | A kind of preparation method of tight type chlorine-resistant composite nanometer filtering film |
| CN108325390A (en) * | 2018-03-08 | 2018-07-27 | 北京林业大学 | A method of improving the compound film properties of polyethyleneimine/sodium lignin sulfonate |
| CN106268374B (en) * | 2015-05-27 | 2018-11-09 | 天津大学 | A kind of solvent-resistant compound nanofiltration membrane and preparation method |
| CN109364759A (en) * | 2018-12-21 | 2019-02-22 | 滁州学院 | A kind of calcium lignosulfonate solvent-resistant compound nanofiltration membrane and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6783711B2 (en) * | 2000-05-23 | 2004-08-31 | Ge Osmonics, Inc. | Process for preparing a sulfonamide polymer matrix |
| US8231013B2 (en) * | 2006-12-05 | 2012-07-31 | The Research Foundation Of State University Of New York | Articles comprising a fibrous support |
-
2020
- 2020-03-09 CN CN202010159127.3A patent/CN111437740B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1356856A1 (en) * | 2002-04-17 | 2003-10-29 | Korea Research Institute Of Chemical Technology | Silicone-coated organic solvent resistant polyamide composite nanofiltration membrane, and method for preparing the same |
| CN103816817A (en) * | 2014-01-28 | 2014-05-28 | 中国科学院化学研究所 | Alkali-resistant cellulose membrane and preparation method thereof |
| CN104759214A (en) * | 2015-03-27 | 2015-07-08 | 北京工业大学 | Preparation method of superhydrophilic/superhydrophobic composite nanofiltration membrane |
| CN106268374B (en) * | 2015-05-27 | 2018-11-09 | 天津大学 | A kind of solvent-resistant compound nanofiltration membrane and preparation method |
| CN105056777A (en) * | 2015-07-16 | 2015-11-18 | 宁波大学 | Lignin-crosslinking modified polymer separation membrane and application thereof |
| CN107261871A (en) * | 2017-08-08 | 2017-10-20 | 北京林业大学 | A kind of preparation method of polyethyleneimine/sodium lignin sulfonate composite membrane |
| CN107899434A (en) * | 2017-09-25 | 2018-04-13 | 浙江理工大学 | A kind of preparation method of tight type chlorine-resistant composite nanometer filtering film |
| CN108325390A (en) * | 2018-03-08 | 2018-07-27 | 北京林业大学 | A method of improving the compound film properties of polyethyleneimine/sodium lignin sulfonate |
| CN109364759A (en) * | 2018-12-21 | 2019-02-22 | 滁州学院 | A kind of calcium lignosulfonate solvent-resistant compound nanofiltration membrane and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| EVALUATION OF PORE STRUCTURE AND ELECTRICAL-PROPERTIES OF NANOFILTRATION MEMBRANES;WANG, XL;《JOURNAL OF CHEMICAL ENGINEERING OF JAPAN》;19950430;第28卷(第2期);186-192 * |
| Optimization of composite nanofiltration membrane through pH control: Application in CuSO4 removal;Ahmad, AL;《SEPARATION AND PURIFICATION TECHNOLOGY》;20060630;第47卷(第3期);162-172 * |
| Shi‐Peng Sun.Enhancement of flux and solvent stability of Matrimid® thin‐film composite membranes for organic solvent nanofiltration.《AIChE Journal》.2014,第60卷(第10期),第3623-3633页. * |
| 以碳酸氢铵为致孔剂的木质素磺酸铵耐溶剂复合纳滤膜的构筑及性能调控研究;石阳;《膜科学与技术》;20191231;第39卷(第06期);87-93 * |
| 界面聚合法制备中空纤维复合纳滤膜;芮玉青;《万方学位论文》;20101231;1、9、17、19、22-28、33 * |
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