CN114130209B - Method for preparing copper alginate hydrogel filtering membrane from waste copper ammonia solution - Google Patents
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- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229940072056 alginate Drugs 0.000 title claims abstract description 63
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 63
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 63
- 239000000017 hydrogel Substances 0.000 title claims abstract description 62
- 235000011114 ammonium hydroxide Nutrition 0.000 title claims abstract description 58
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 53
- 239000010949 copper Substances 0.000 title claims abstract description 53
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 238000001914 filtration Methods 0.000 title claims abstract description 31
- 239000012528 membrane Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 28
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 28
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000661 sodium alginate Substances 0.000 claims abstract description 22
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 22
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 238000007790 scraping Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 230000003115 biocidal effect Effects 0.000 claims abstract description 4
- 238000010612 desalination reaction Methods 0.000 claims abstract description 4
- 239000010865 sewage Substances 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 230000001112 coagulating effect Effects 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- 238000005266 casting Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000648 calcium alginate Substances 0.000 description 4
- 235000010410 calcium alginate Nutrition 0.000 description 4
- 229960002681 calcium alginate Drugs 0.000 description 4
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical class [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention reports a method for preparing a copper alginate hydrogel filtering membrane by using a waste copper ammonia solution. Firstly, dissolving sodium alginate by using a waste copper ammonia solution to obtain a casting solution. Scraping the casting solution into a film, and then soaking the film into an acid solution. The copper ammonia solution releases copper ions when encountering acid, and the copper ions are immediately crosslinked with alginate to form the copper alginate hydrogel film. The formed copper alginate hydrogel film is soaked in a weak alkaline solution, and acid solution in the hydrogel is removed by alkali neutralization acid, so that carboxyl groups on the alginate are fully ionized, and the copper ions are fully crosslinked with the carboxyl groups on the alginate. And finally, washing the hydrogel film with deionized water to remove redundant ions, thereby obtaining the copper alginate hydrogel filtering film prepared from the waste copper ammonia solution. The preparation method is simple, waste is changed into valuable, and the obtained copper alginate hydrogel filtering membrane has good antibacterial property and has wide application prospect in the fields of sewage treatment, dye desalination, dye interception, antibiotic removal and the like.
Description
Technical Field
The invention relates to a method for preparing a copper alginate hydrogel filtering membrane by using a waste copper ammonia solution, belonging to the field of functional materials and membrane separation.
The invention relates to the technical fields of waste copper ammonia solution, filtering membrane, hydrogel and the like. In particular to a method for preparing a copper alginate hydrogel filtering membrane by using waste copper ammonia solution.
Background
The cuprammonium solution is an old cellulose solvent, can be used for preparing regenerated cellulose products such as artificial fibers, hollow fibers, non-woven fabrics and the like, but researches on preparing other functional new materials by using the cuprammonium solution have been reported. The cellulose cuprammonium solution contains a large amount of copper, and has great cost and application advantages in preparing copper composite materials.
Sodium alginate is a natural polysaccharide, and is concerned because of its strong hydrophilic ability, and more importantly, it has excellent environmental resistance under high acid and alkali conditions, better than most common hydrogels, and better anti-pollution performance. In our previous research, a series of calcium alginate-based hydrogel filtration membranes (patent nos. ZL201310424398.7, ZL201310424399.1 and ZL 201310424397.2) were prepared, but these calcium alginate hydrogel filtration membranes have the problems of low mechanical strength, easy swelling, easy bacteria breeding, low permeation flux, etc., so it is important to construct a hydrogel membrane with high strength, swelling resistance, good antibacterial performance and high flux.
Copper ions have stronger affinity with sodium alginate, have good antibacterial activity and higher environmental safety, and compared with a general silver antibacterial auxiliary agent, the copper antibacterial auxiliary agent gradually attracts importance of scientific researchers due to excellent antibacterial performance and low cost, and has good application prospect in the fields of biomedicine and the like. Copper ions are protected in a copper ammonia solution complexing mode, and then the copper ions are released by an acid solution, so that the effect of releasing copper ions to crosslink alginate in situ is achieved, the crosslinking effect of the generated hydrogel film is better, and the performance of each part of the film is more uniform.
The invention reports a method for preparing a copper alginate hydrogel filtering membrane by using a waste copper ammonia solution. Firstly, dissolving sodium alginate by using a waste copper ammonia solution to obtain a casting solution. Scraping the casting solution into a film, and then soaking the film into an acid solution. The copper ammonia solution releases copper ions when encountering acid, and the copper ions are immediately crosslinked with alginate to form the copper alginate hydrogel film. The formed copper alginate hydrogel film is soaked in a weak alkaline solution, and acid solution in the hydrogel is removed by alkali neutralization acid, so that carboxyl groups on the alginate are fully ionized, and the copper ions are fully crosslinked with the carboxyl groups on the alginate. And finally, washing the hydrogel film with deionized water to remove redundant ions, thereby obtaining the copper alginate hydrogel filtering film prepared from the waste copper ammonia solution. The preparation method is simple, waste is changed into valuable, and the obtained copper alginate hydrogel filtering membrane has good antibacterial property and has wide application prospect in the fields of sewage treatment, dye desalination, dye interception, antibiotic removal and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problems that the waste copper ammonia solution pollutes the environment, the calcium alginate hydrogel is not antibacterial, the stability is poor and the like.
The invention solves the problems that the waste copper ammonia solution pollutes the environment, calcium alginate hydrogel is not antibacterial, has poor stability and the like, and provides a method for preparing a copper alginate hydrogel filtering membrane by using the waste copper ammonia solution.
The invention provides a method for preparing a copper alginate hydrogel filtering membrane by using a waste copper ammonia solution, which is characterized by comprising the following steps:
a) Firstly, filtering a waste copper ammonia solution to remove insoluble substances in the copper ammonia solution, respectively adding an enhancer and sodium alginate into the filtered waste copper ammonia solution, mixing, dissolving and dispersing uniformly to obtain a mixture aqueous solution with the mass percent concentration of sodium alginate of 0.1-10% and the mass percent concentration of the enhancer of 0.01-10%, and defoaming for later use;
b) Preparing an acid solution as a coagulation bath;
c) Pouring the mixture aqueous solution obtained in the step a) after standing and defoaming onto a clean glass plate, scraping the glass plate and a scraped film by using a glass rod with copper wires wound at two ends and having the diameter of 10-1000 mu m, immediately soaking the glass plate and the scraped film into the coagulating bath obtained in the step b), releasing copper ions when the copper ammonia solution encounters acid in the coagulating bath, and immediately crosslinking the copper ions with sodium alginate to generate a copper alginate hydrogel film;
d) Immersing the formed copper alginate hydrogel film in a weak alkaline solution, and removing acid solution in the copper alginate hydrogel by alkali neutralization acid to fully ionize carboxyl groups on the alginate, so that the carboxyl groups on the alginate are fully crosslinked by copper ions; and finally, washing the hydrogel film with deionized water to remove redundant ions, thereby obtaining the copper alginate hydrogel filtering film prepared from the waste copper ammonia solution.
The reinforcing agent is any one or a mixture of two or more of titanium dioxide, carboxylated multiwall carbon nanotubes, graphene oxide and halloysite; the acid solution is any one or a mixture of two or more of hydrochloric acid, sulfuric acid, nitric acid and acetic acid; the weak alkaline solution is any one or a mixture of two or more of ammonia water, sodium carbonate, sodium bicarbonate and calcium hydroxide.
The membrane obtained by the invention has wide application prospect in the fields of sewage treatment, dye desalination, dye interception, antibiotic removal and the like.
Detailed Description
Specific embodiments of the present invention are described below, but the present invention is not limited by the embodiments.
Example 1.
a) Firstly, filtering a waste copper ammonia solution to remove insoluble substances in the copper ammonia solution, respectively adding titanium dioxide and sodium alginate into the filtered waste copper ammonia solution, mixing, dissolving and dispersing uniformly to obtain a mixture aqueous solution with the mass percent concentration of the sodium alginate of 0.1% and the mass percent concentration of the titanium dioxide of 0.01%, and defoaming for later use;
b) Preparing hydrochloric acid as a coagulating bath;
c) Pouring the mixture aqueous solution obtained in the step a) after standing and defoaming onto a clean glass plate, scraping the glass plate and a scraped film by using a glass rod with 10 mu m-diameter copper wires wound at two ends, and immediately soaking the glass plate and the scraped film into the coagulating bath obtained in the step b), wherein copper ions are released by the copper ammonia solution when the copper ammonia solution encounters acid in the coagulating bath, and the copper ions are immediately crosslinked with sodium alginate to generate a copper alginate hydrogel film;
d) Immersing the formed copper alginate hydrogel film in ammonia water, and removing hydrochloric acid in the copper alginate hydrogel by alkali neutralization acid to fully ionize carboxyl groups on the alginate, so that the carboxyl groups on the alginate are fully crosslinked by copper ions; and finally, washing the hydrogel film with deionized water to remove redundant ions, thereby obtaining the copper alginate hydrogel filtering film prepared from the waste copper ammonia solution.
Example 2.
a) Firstly, filtering a waste copper ammonia solution to remove insoluble substances in the copper ammonia solution, respectively adding carboxylated multiwall carbon nanotubes and sodium alginate into the filtered waste copper ammonia solution, mixing, dissolving and dispersing uniformly to obtain a mixture aqueous solution with the mass percent concentration of the sodium alginate being 1% and the mass percent concentration of the titanium dioxide being 0.1%, and defoaming for later use;
b) Preparing sulfuric acid as a coagulating bath;
c) Pouring the mixture aqueous solution obtained in the step a) after standing and defoaming onto a clean glass plate, scraping the glass plate and a scraped film by using a glass rod with copper wires wound at two ends and having the diameter of 100 mu m, immediately soaking the glass plate and the scraped film into the coagulating bath obtained in the step b), releasing copper ions when the copper ammonia solution encounters acid in the coagulating bath, and immediately crosslinking the copper ions with sodium alginate to generate a copper alginate hydrogel film;
d) Immersing the formed copper alginate hydrogel film in sodium carbonate, and removing hydrochloric acid in the copper alginate hydrogel by alkali neutralization acid to fully ionize carboxyl groups on the alginate, so that the carboxyl groups on the alginate are fully crosslinked by copper ions; and finally, washing the hydrogel film with deionized water to remove redundant ions, thereby obtaining the copper alginate hydrogel filtering film prepared from the waste copper ammonia solution.
Example 3.
a) Firstly, filtering a waste copper ammonia solution, removing insoluble substances in the copper ammonia solution, respectively adding graphene oxide and sodium alginate into the filtered waste copper ammonia solution, mixing, dissolving and dispersing uniformly to obtain a mixture aqueous solution with the mass percent concentration of sodium alginate of 2% and the mass percent concentration of titanium dioxide of 1%, and defoaming for later use;
b) Preparing nitric acid as a coagulating bath;
c) Pouring the mixture aqueous solution obtained in the step a) after standing and defoaming onto a clean glass plate, scraping the glass plate and a scraped film by using a glass rod with 200 mu m-diameter copper wires wound at two ends, and immediately soaking the glass plate and the scraped film into the coagulating bath obtained in the step b), wherein copper ions are released by the copper ammonia solution when the copper ammonia solution encounters acid in the coagulating bath, and the copper ions are immediately crosslinked with sodium alginate to generate a copper alginate hydrogel film;
d) Soaking the formed copper alginate hydrogel film into sodium bicarbonate, and removing hydrochloric acid in the copper alginate hydrogel by alkali neutralization acid to fully ionize carboxyl groups on the alginate, so that the carboxyl groups on the alginate are fully crosslinked by copper ions; and finally, washing the hydrogel film with deionized water to remove redundant ions, thereby obtaining the copper alginate hydrogel filtering film prepared from the waste copper ammonia solution.
Example 4.
a) Firstly, filtering a waste copper ammonia solution to remove insoluble substances in the copper ammonia solution, respectively adding halloysite and sodium alginate into the filtered waste copper ammonia solution, mixing, dissolving and dispersing uniformly to obtain a mixture aqueous solution with the mass percent concentration of sodium alginate of 10% and the mass percent concentration of titanium dioxide of 10%, and defoaming for later use;
b) Preparing acetic acid as a coagulation bath;
c) Pouring the mixture aqueous solution obtained in the step a) after standing and defoaming onto a clean glass plate, scraping the glass plate and a scraped film by using a glass rod with two ends wound with copper wires with the diameter of 1000 mu m, and immediately soaking the glass plate and the scraped film into the coagulating bath obtained in the step b), wherein copper ions are released by the copper ammonia solution when the copper ammonia solution encounters acid in the coagulating bath, and the copper ions are immediately crosslinked with sodium alginate to generate a copper alginate hydrogel film;
d) Immersing the formed copper alginate hydrogel film in calcium hydroxide, and removing hydrochloric acid in the copper alginate hydrogel by alkali neutralization acid to fully ionize carboxyl groups on the alginate, so that the carboxyl groups on the alginate are fully crosslinked by copper ions; and finally, washing the hydrogel film with deionized water to remove redundant ions, thereby obtaining the copper alginate hydrogel filtering film prepared from the waste copper ammonia solution.
Claims (4)
1. The method for preparing the copper alginate hydrogel filtering membrane by using the waste copper ammonia solution is characterized by comprising the following steps of:
a) Firstly, filtering a waste copper ammonia solution to remove insoluble substances in the copper ammonia solution, respectively adding an enhancer and sodium alginate into the filtered waste copper ammonia solution, mixing, dissolving and dispersing uniformly to obtain a mixture aqueous solution with the mass percent concentration of sodium alginate of 0.1-10% and the mass percent concentration of the enhancer of 0.01-10%, and defoaming for later use; the reinforcing agent is any one or a mixture of two or more of titanium dioxide, carboxylated multi-wall carbon nanotubes, graphene oxide and halloysite;
b) Preparing an acid solution as a coagulation bath;
c) Pouring the mixture aqueous solution obtained in the step a) after standing and defoaming onto a clean glass plate, scraping the glass plate and a scraped film by using a glass rod with copper wires wound at two ends and having the diameter of 10-1000 mu m, immediately soaking the glass plate and the scraped film into the coagulating bath obtained in the step b), releasing copper ions when the copper ammonia solution encounters acid in the coagulating bath, and immediately crosslinking the copper ions with sodium alginate to generate a copper alginate hydrogel film;
d) Immersing the formed copper alginate hydrogel film in a weak alkaline solution, and removing acid solution in the copper alginate hydrogel by alkali neutralization acid to fully ionize carboxyl groups on the alginate, so that the carboxyl groups on the alginate are fully crosslinked by copper ions; and finally, washing the hydrogel film with deionized water to remove redundant ions, thereby obtaining the copper alginate hydrogel filtering film prepared from the waste copper ammonia solution.
2. The method for preparing the copper alginate hydrogel filtering membrane by using the waste copper ammonia solution as claimed in claim 1, wherein the acid solution is any one or a mixture of two or more of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
3. The method for preparing the copper alginate hydrogel filtering membrane by using the waste copper ammonia solution as claimed in claim 1, wherein the weak alkaline solution is any one or a mixture of two or more of ammonia water, sodium carbonate, sodium bicarbonate and calcium hydroxide.
4. The use of a membrane obtained by the method for preparing a copper alginate hydrogel filtration membrane from a waste copper ammonia solution according to claim 1 in sewage treatment, dye desalination, dye interception, antibiotic removal.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09279412A (en) * | 1996-04-10 | 1997-10-28 | Asahi Chem Ind Co Ltd | Copper ammonia cellulose dope |
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2021
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| JPH09279412A (en) * | 1996-04-10 | 1997-10-28 | Asahi Chem Ind Co Ltd | Copper ammonia cellulose dope |
| US5962005A (en) * | 1997-04-17 | 1999-10-05 | Rengo Co., Ltd | Transparent cellulose hydrogel and production process thereof |
| CN101007240A (en) * | 2006-01-26 | 2007-08-01 | 中国科学院大连化学物理研究所 | Cellulose asymmetric hollow fiber ultrafiltration membranes and preparation method thereof |
| CN103464217A (en) * | 2013-09-13 | 2013-12-25 | 天津工业大学 | Alginate-based composite hydrogel catalytic membrane of renewable catalyst and preparation method thereof |
| CN108048933A (en) * | 2017-11-20 | 2018-05-18 | 河北吉藁化纤有限责任公司 | A kind of copper-bearing antibacterial viscose rayon and preparation method thereof |
| CN111359549A (en) * | 2020-03-12 | 2020-07-03 | 上海交通大学 | Preparation method of composite hydrogel and aerogel |
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