CN113509907B - Preparation of lignin-based composite hydrogel and application of lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials - Google Patents
Preparation of lignin-based composite hydrogel and application of lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 117
- 229920005610 lignin Polymers 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 52
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005457 ice water Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 50
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- LEOJISUPFSWNMA-UHFFFAOYSA-N ABEI Chemical compound O=C1NNC(=O)C=2C1=CC(N(CCCCN)CC)=CC=2 LEOJISUPFSWNMA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 9
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 25
- 238000004020 luminiscence type Methods 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 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 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241000218378 Magnolia Species 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 206010027439 Metal poisoning Diseases 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 208000008127 lead poisoning Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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Abstract
The invention discloses a preparation method of lignin-based composite hydrogel and application of lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials, and belongs to the field of functional materials. The preparation method of the hydrogel comprises the following steps: 1) Uniformly mixing sodium hydroxide aqueous solution and acrylic acid under the ice water bath condition, then sequentially adding lignin sulfonate, N-methylene bisacrylamide and potassium persulfate, and uniformly stirring. 2) And (3) carrying out free radical polymerization reaction on the obtained mixed solution under the ultrasonic auxiliary condition, soaking the obtained product in absolute ethyl alcohol overnight, and freeze-drying to obtain the lignin-based composite hydrogel. The invention can fully utilize lignin, which is an industrial waste, and provides a new way for the high-value utilization of lignin, and the prepared hydrogel has extremely strong adsorption capacity on heavy metal ions in water. In addition, the hydrogel after absorbing heavy metal ions can be applied to preparing luminescent materials. Therefore, the method has good application prospect.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to preparation of lignin-based composite hydrogel and application of lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials.
Background
Along with the promotion of the industrialization progress, industries such as mining, smelting, electronics, electroplating, petroleum, fertilizer manufacturing and the like can generate a large amount of wastewater rich in heavy metal ions. The discharge of such wastewater has resulted in the enrichment of heavy metal ions in natural bodies of water. Heavy metal ions can not be degraded, so that the heavy metal ions are extremely easy to enter human bodies through food chains, and further the health of human bodies is seriously endangered, such as cadmium pollution events in Guangxi province, lead events in Jiangsu blood, lead poisoning events in Shanxi province and the like. Therefore, how to quickly and efficiently remove heavy metal ions in water body has become a great subject in the current water pollution control research field.
At present, the method for removing heavy metal ions in water is mainly divided into a chemical method, a biological method and a physical adsorption method. In contrast, the physical adsorption method is highly focused by a large number of students because of the advantages of simple operation, low cost, no secondary pollution and the like. The key point of using physical adsorption method is to develop cheap and efficient adsorption material. Currently, adsorbent materials that have been developed mainly include activated carbon, zeolite, resin, and hydrogel. The hydrogel is a novel three-dimensional network structure material, contains a large number of functional groups such as hydroxyl, amino or carboxyl, and the functional groups can be effectively chelated with heavy metal ions in a water body, so that the hydrogel has excellent adsorption performance. However, most of the current hydrogel materials are made from non-renewable chemicals, and often require a large amount of organic solvents, such as dimethyl sulfoxide, glycerol ether, etc., to be used in the preparation process. This not only increases the cost of the preparation of the hydrogel, but also causes serious environmental pollution, which is unfavorable for the industrial application. In addition, in the current research, hydrogels after adsorbing heavy metal ions are often directly treated as solid waste, which causes serious waste of resources.
Disclosure of Invention
Aiming at the defects in the preparation and application of the existing heavy metal ion adsorption material, the invention provides the preparation of lignin-based composite hydrogel and the application of lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials. The invention takes industrial lignin and acrylic acid monomers as raw materials, prepares lignin-based composite hydrogel by an ultrasonic assisted free radical polymerization method, and then applies the lignin-based composite hydrogel to the fields of heavy metal ion adsorption and luminescent materials. The invention not only provides a new way for the high-value utilization of industrial lignin, but also the prepared adsorbent has extremely strong adsorption capacity on heavy metal ions in water. In addition, the hydrogel after absorbing heavy metal ions can be developed into a luminescent material with high luminous intensity and long duration. Therefore, the invention has good application prospect.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the lignin-based composite hydrogel comprises the following steps:
1) Uniformly mixing sodium hydroxide aqueous solution and acrylic acid under the ice water bath condition, then sequentially adding lignin sulfonate, N-methylene bisacrylamide and potassium persulfate, and uniformly stirring.
2) And (3) carrying out free radical polymerization reaction on the mixed solution obtained in the step (1) under the ultrasonic auxiliary condition, soaking the obtained product in absolute ethyl alcohol overnight, and then freeze-drying to obtain the lignin-based composite hydrogel.
According to the above technical solution, in a preferred case, in step 1), the lignosulfonate is sodium lignosulfonate.
According to the above technical scheme, in the preferred case, in the step 1), the concentration of the sodium hydroxide aqueous solution is 5-10 mol/L, preferably 7-8 mol/L; the volume ratio of the sodium hydroxide aqueous solution to the acrylic acid is 1:1.
according to the above technical solution, in the preferred case, in step 1), the ratio of acrylic acid, lignin sulfonate, N-methylenebisacrylamide to potassium persulfate is 3mL:0.1 to 1.5g:0.01 to 0.03g:0.1 to 0.3g, preferably 3mL:0.5 to 1.0g:0.01 to 0.02g: 0.1-0.2 g.
According to the above technical scheme, in a preferred case, in the step 2), the temperature of the free radical polymerization reaction is 40-80 ℃, preferably 50-60 ℃; the time is 1 to 3 hours, preferably 1 to 2 hours.
According to the above technical scheme, in a preferred case, in the step 2), the temperature of freeze drying is-50 to-60 ℃, preferably-50 ℃; the time is 20 to 40 hours, preferably 24 hours.
According to the technical scheme, in the step 2), the ultrasonic auxiliary condition is preferably 200-300W and 30-50 kHz.
The invention also relates to a lignin-based composite hydrogel prepared by the method.
The application of the lignin-based composite hydrogel in heavy metal ion adsorption comprises the following steps: mixing the lignin-based composite hydrogel with heavy metal ion aqueous solution, and adsorbing for 10-30 hours in a shaking table at 50-150 rpm at 20-40 ℃; after the adsorption is finished, carrying out suction filtration, and measuring the concentration of heavy metal ions in filtrate by an atomic absorption method; the obtained solid sample is lignin-based composite hydrogel after heavy metal ions are adsorbed.
According to the above technical solution, in a preferred case, the heavy metal ion aqueous solution is one or more of cobalt chloride solution, cobalt nitrate solution, copper chloride solution, copper nitrate solution, nickel chloride solution, nickel nitrate solution, cadmium chloride solution, cadmium nitrate solution, and lead nitrate solution, and is preferably cobalt chloride solution, nickel nitrate solution, or cadmium nitrate solution. The concentration of the heavy metal ion aqueous solution is 10-400 mg/L.
According to the above technical solution, preferably, the ratio of the lignin-based composite hydrogel to the heavy metal ion aqueous solution is 0.1g:50 to 100mL, preferably 0.1g:50mL.
The application of the lignin-based composite hydrogel in the field of luminescent materials is that the lignin-based composite hydrogel after heavy metal ions are adsorbed, which is obtained by the method, and the application process of the lignin-based composite hydrogel after heavy metal ions are as follows: and mixing the lignin-based composite hydrogel adsorbed with heavy metal ions with an N- (4-aminobutyl) -N-ethyl isoluminol solution, uniformly stirring, and adding a hydrogen peroxide solution to obtain the chemiluminescent hydrogel with high luminous intensity and long duration.
According to the above technical scheme, preferably, the lignin-based composite hydrogel after heavy metal ion adsorption is fully crushed, ground or smashed and then mixed with the N- (4-aminobutyl) -N-ethyl isoluminol solution.
According to the above technical scheme, preferably, the concentration of the N- (4-aminobutyl) -N-ethyl isoluminol solution is 1.0-25.0 mmol/L, preferably 5.0-10.0 mmol/L; the concentration of the hydrogen peroxide solution is 0.01-0.2 mol/L, preferably 0.05-0.1 mol/L; the ratio of the lignin-based composite hydrogel, the N- (4-aminobutyl) -N-ethyl isoluminol solution and the hydrogen peroxide solution after heavy metal ions are adsorbed is 0.1g:0.1 to 0.3mL:0.1 to 0.3mL, preferably 0.1g: 0.2-0.3 mL: 0.2-0.3 mL.
Compared with the prior art, the invention has the following advantages:
1) The raw material used in the invention is the byproduct lignosulfonate in the pulping and papermaking process, but is not limited to the lignin, so the raw material used in the invention has rich sources and low price, and is suitable for large-scale industrial utilization.
2) The preparation method of the hydrogel is simple and green, does not use any organic solvent, and can be produced in large scale.
3) The hydrogel prepared by the invention contains abundant heavy metal ion adsorption sites, so that the hydrogel has strong adsorption capacity on various heavy metal ions.
4) The hydrogel after absorbing heavy metal ions is applied to the preparation of luminescent materials for the first time, and the obtained luminescent hydrogel has the advantages of high luminous intensity, long luminous time and the like, and can be applied to cold light sources, decorative entertainment and underwater illumination in emergency.
5) The invention prepares the hydrogel by utilizing the industrial lignin and applies the hydrogel to the fields of heavy metal ion adsorption and luminescent materials, which not only can fully utilize the lignin, namely industrial waste, and provides a new way for the high-value utilization of the lignin, but also the prepared hydrogel has extremely strong adsorption capacity on heavy metal ions in water. In addition, the hydrogel after absorbing heavy metal ions can be applied to preparing luminescent materials. Therefore, the method has good application prospect.
Drawings
FIG. 1 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 ) Co of (C) 2+ Ion adsorption data.
FIG. 2 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 ) Cu of (2) 2+ Ion adsorption data.
FIG. 3 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention 3 ) Co of (C) 2+ 、Cu 2+ 、Ni 2 + 、Pb 2+ And Cd 2+ Ion adsorption data.
FIG. 4 is a graph showing the luminescence intensity and luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 7 of the present invention.
FIG. 5 is a graph showing the luminescence intensity and luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 8 of the present invention.
FIG. 6 is a graph showing the luminescence intensity and luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 9 of the present invention.
FIG. 7 is a digital photograph of the lignin-based composite luminescent hydrogel prepared in example 10 of the present invention under dark conditions for different luminescent durations.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the scope of the present invention is not limited to the embodiments.
Example 1
The preparation method of the lignin-based composite hydrogel comprises the following steps:
1) 3mL of aqueous sodium hydroxide solution (10 mol/L) and 3mL of acrylic acid were mixed uniformly under ice-water bath conditions, and then 0.3g, 0.6g, 0.9g, 1.2g of sodium lignin sulfonate (Shanghai Meilin Biochemical Co., ltd.), 0.02g of N, N-methylenebisacrylamide and 0.2g of potassium persulfate were added, respectively, and magnetically stirred at a rotation speed of 300rpm for 5 minutes to completely dissolve.
2) The mixed solution obtained in the step 1) is put into an ultrasonic cleaner (250W, 40 kHz) at 50 ℃ to carry out free radical polymerization for 1 h. After the reaction was completed, the obtained product was immersed in absolute ethanol overnight.
3) Filtering the product obtained in the step 2), placing the filtered product into an ultralow temperature refrigerator (-52 ℃), taking out the filtered product after 6 hours, placing the filtered product into a freeze dryer (-50 ℃), and taking out a freeze-dried sample after 24 hours, namely ligninBased composite hydrogel (Lignosulfonate in amounts of 0.3g, 0.6g, 0.9g and 1.2g were designated SL-g-PAA, respectively) 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 )。
Example 2
The preparation method of the lignin-based composite hydrogel comprises the following steps:
1) 3mL of aqueous sodium hydroxide (7.5 mol/L) and 3mL of acrylic acid were mixed uniformly under ice-water bath conditions, then 0.9g of sodium lignin sulfonate (Shanghai Michelia Biochemical Co., ltd.), 0.01g of N, N-methylenebisacrylamide and 0.2g of potassium persulfate were sequentially added, and magnetically stirred at 300rpm for 5 minutes to completely dissolve.
2) The mixed solution obtained in the step 1) was placed in an ultrasonic cleaner (250W, 40 kHz) at 50, 60, 70 and 80℃respectively, and radical polymerization was carried out for 1 hour. After the reaction was completed, the obtained product was immersed in absolute ethanol overnight.
3) Filtering the product obtained in the step 2), placing the filtered product in an ultralow temperature refrigerator (-52 ℃), taking out the filtered product after 6 hours, placing the filtered product in a freeze dryer (-50 ℃), taking out the filtered product after 24 hours, and taking out the filtered product, thus obtaining lignin-based composite hydrogel (the free radical polymerization reaction temperature is 50 ℃, 60 ℃, 70 ℃ and 80 ℃ are respectively marked as SL-g-PAA 5 、SL-g-PAA 6 、SL-g-PAA 7 And SL-g-PAA 8 )。
Example 3
The preparation method of the lignin-based composite hydrogel comprises the following steps:
1) 3mL of aqueous sodium hydroxide (7.5 mol/L) and 3mL of acrylic acid were mixed uniformly under ice-water bath conditions, then 0.6g of sodium lignin sulfonate (Shanghai Michelia Biochemical Co., ltd.), 0.01g of N, N-methylenebisacrylamide and 0.2g of potassium persulfate were sequentially added, and magnetically stirred at 300rpm for 5 minutes to completely dissolve.
2) The mixed solution obtained in the step 1) was put into an ultrasonic cleaner (250W, 40 kHz) at 50℃to carry out radical polymerization for 1h,2h and 3h, respectively. After the reaction was completed, the obtained product was immersed in absolute ethanol overnight.
3) The step 2) is carried outFiltering the product, placing into an ultralow temperature refrigerator (-52 ℃) for 6 hours, taking out, placing into a freeze dryer (-50 ℃) for 24 hours, and taking out a freeze-dried sample, namely the lignin-based composite hydrogel (the free radical polymerization reaction time is 1 hour, 2 hours and 3 hours are respectively marked as SL-g-PAA) 9 、SL-g-PAA 10 And SL-g-PAA 11 )。
Example 4
Lignin-based composite hydrogel (SL-g-PAA) prepared by example 1 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 ) Co in water 2+ An ion adsorption experiment comprising the steps of:
1) 0.1g of SL-g-PAA prepared in example 1 was weighed out separately 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 The hydrogel was placed in a 100mL Erlenmeyer flask, then 50mL cobalt chloride solution (200 mg Co/L) was added, and the Erlenmeyer flask was finally sealed.
2) Placing the conical flask obtained in step 1) into a constant temperature shaking table, oscillating at 25deg.C and 150rpm for 24 hr, filtering with 0.22 μm filter membrane, and measuring Co in the filtrate by atomic absorption method 2+ Ion concentration. The obtained solid sample is lignin-based composite hydrogel after ion adsorption, and is respectively marked as follows: co (Co) 2+ @SL-g-PAA 1 、Co 2+ @SL-g-PAA 2 、Co 2+ @SL-g-PAA 3 And Co 2+ @SL-g-PAA 4 。
3) According to Co in aqueous solution before and after adsorption 2+ Ion concentration calculation of Co of adsorbent 2+ Ion adsorption amount (as shown in fig. 1).
Example 5
Lignin-based composite hydrogel (SL-g-PAA) prepared by example 1 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 ) Cu in water body 2+ An ion adsorption experiment comprising the steps of:
1) 0.1g of SL-g-PAA prepared in example 1 was weighed out separately 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 The hydrogel is put into a 100mL conical flask, and then 50mL of copper nitrate solution is added200mg Cu/L), and finally the flask was sealed.
2) Placing the conical flask obtained in step 1) into a constant temperature shaking table, oscillating at 25deg.C and 150rpm for 24 hr, filtering with 0.22 μm filter membrane, and measuring Cu in the filtrate by atomic absorption method 2+ Ion concentration. The obtained solid sample is the adsorbed Cu 2+ The lignin-based composite hydrogel after ions is respectively marked as: cu (Cu) 2+ @SL-g-PAA 1 、Cu 2+ @SL-g-PAA 2 、Cu 2+ @SL-g-PAA 3 And Cu 2+ @SL-g-PAA 4 。
3) According to Cu in the aqueous solution before and after adsorption 2+ Ion concentration calculation of Cu of adsorbent 2+ Ion adsorption amount (as shown in fig. 2).
Example 6
Lignin-based composite hydrogel (SL-g-PAA) prepared by example 1 3 ) Co in water body is respectively carried out 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ And Cd 2+ An ion adsorption experiment comprising the steps of:
1) 0.1g of SL-g-PAA prepared in example 1 was weighed out 3 The hydrogel was placed in a 100mL Erlenmeyer flask, then 50mL of cobalt chloride solution (400 mg Co/L), 50mL of copper nitrate solution (400 mg Cu/L), 50mL of nickel nitrate solution (400 mg Ni/L), 50mL of lead nitrate solution (400 mg Pb/L), and 50mL of cadmium nitrate solution (400 mg Cd/L) were added, respectively, and finally the Erlenmeyer flask was sealed.
2) Placing the conical flask obtained in step 1) into a constant temperature shaking table, oscillating at 25deg.C and 150rpm for 24 hr, filtering with 0.22 μm filter membrane, and measuring Co in the filtrate by atomic absorption method 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ And Cd 2+ Ion concentration. The obtained solid samples are respectively Co-adsorbed 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ And Cd 2+ The lignin-based composite hydrogel after ions is respectively marked as: co (Co) 2+ @SL-g-PAA 3 、Cu 2+ @SL-g-PAA 3 、Ni 2+ @SL-g-PAA 3 、Pb 2+ @SL-g-PAA 3 And Cd 2+ @SL-g-PAA 3 。
3) Calculating according to the change of the concentration of heavy metal ions in the aqueous solution before and after adsorption to obtain SL-g-PAA 3 The adsorption amount of each heavy metal ion (as shown in FIG. 3).
Example 7
Co adsorption obtained in example 4 was used 2+ Post-ionic lignin-based composite hydrogels (Co 2+ @SL-g-PAA 3 ) Preparing a luminescent hydrogel material, comprising the steps of:
1) 0.1g of Co obtained in example 4 was weighed out 2+ @SL-g-PAA 3 The mixture was put into a mortar and sufficiently ground. The resulting solid was then mixed with 0.1mL of N- (4-aminobutyl) -N-ethyl isoluminol solutions of different concentrations (1 mmol/L, 2.5mmol/L, 5mmol/L, 10mmol/L and 15 mmol/L), respectively.
2) The mixture obtained in the step 1) was magnetically stirred for 5 hours, and then 0.3mL of hydrogen peroxide solution (0.1 mol/L) was slowly added to obtain a series of chemiluminescent hydrogel materials. Finally, the resulting luminescent gel material was put into a BPCL weak luminescence analyzer (PMT voltage of 800V), and its luminescence intensity and luminescence kinetics were measured (as shown in fig. 4).
Example 8
Co adsorption obtained in example 4 was used 2+ Post-ionic lignin-based composite hydrogels (Co 2+ @SL-g-PAA 3 ) Preparing a luminescent hydrogel material, comprising the steps of:
1) 0.1g of Co obtained in example 4 was weighed out 2+ @SL-g-PAA 3 The mixture was put into a mortar and sufficiently ground. The resulting solid was then mixed with 0.1mL of N- (4-aminobutyl) -N-ethyl isoluminol solution (5 mmol/L).
2) Magnetically stirring the mixture obtained in the step 1) for 3 hours, and then adding 0.3mL of hydrogen peroxide solutions with different concentrations (0.025 mol/L, 0.05mol/L, 0.075mol/L, 0.1mol/L and 0.125 mol/L) respectively to obtain a series of chemiluminescent hydrogel materials. Finally, the resulting luminescent gel material was put into a BPCL weak luminescence analyzer (PMT voltage of 800V), and its luminescence intensity and luminescence kinetics were measured (as shown in fig. 5).
Example 9
By means ofLignin-based composite hydrogel (SL-g-PAA) before and after heavy metal ion adsorption in example 6 3 、Co 2+ @SL-g-PAA 3 、Cu 2+ @SL-g-PAA 3 、Ni 2+ @SL-g-PAA 3 、Pb 2+ @SL-g-PAA 3 And Cd 2+ @SL-g-PAA 3 ) Preparing a luminescent hydrogel material, comprising the steps of:
1) 0.1g of SL-g-PAA from example 6 was weighed out separately 3 (control), co 2+ @SL-g-PAA 3 、Cu 2+ @SL-g-PAA 3 、Ni 2+ @SL-g-PAA 3 、Pb 2+ @SL-g-PAA 3 And Cd 2+ @SL-g-PAA 3 The mixture was put into a mortar and sufficiently ground. The resulting solid was then mixed with 0.1mL of N- (4-aminobutyl) -N-ethyl isoluminol solution (5 mmol/L).
2) The mixture obtained in the step 1) was magnetically stirred for 3 hours, and then 0.3mL of hydrogen peroxide solution (0.1 mol/L) was added to obtain a series of chemiluminescent hydrogel materials. Finally, the resulting luminescent gel material was put into a BPCL weak luminescence analyzer (PMT voltage of 800V), and its luminescence intensity and luminescence kinetics were measured (as shown in fig. 6).
Example 10
Co adsorption obtained in example 4 was used 2+ Post-ionic lignin-based composite hydrogels (Co 2+ @SL-g-PAA 3 ) Preparing a luminescent hydrogel material, comprising the steps of:
1) 1g of Co obtained in example 4 was weighed out 2+ @SL-g-PAA 3 The mixture was put into a mortar and sufficiently ground. The resulting solid was then mixed with 1mL of N- (4-aminobutyl) -N-ethyl isoluminol solution (15 mmol/L).
2) Magnetically stirring the mixture obtained in the step 1) for 3 hours, and then adding 3mL of hydrogen peroxide solution (0.1 mol/L) to obtain the chemiluminescent hydrogel material. Finally, the chemiluminescent duration of the luminescent hydrogel material was observed in a dark environment (as shown in FIG. 7).
FIG. 1 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 ) A kind of electronic deviceCo 2+ Ion adsorption data. As can be seen from the figure, the composite hydrogel is opposite to Co with the increase of the dosage of lignosulfonate 2+ The ion adsorption amount gradually decreases. However, when the addition amount of the lignosulfonate reaches 0.9g, the composite hydrogel still has higher Co 2+ Ion adsorption capacity.
FIG. 2 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention 1 、SL-g-PAA 2 、SL-g-PAA 3 And SL-g-PAA 4 ) Cu of (2) 2+ Ion adsorption data. As can be seen from the figure, the composite hydrogel has the effect of Cu with the increase of the dosage of lignosulfonate 2+ The ion adsorption amount gradually decreases. However, when the addition amount of the lignosulfonate reaches 0.9g, the composite hydrogel still has higher Cu 2+ Ion adsorption capacity.
FIG. 3 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention 3 ) Co of (C) 2+ 、Cu 2+ 、Ni 2 + 、Pb 2+ And Cd 2+ Ion adsorption data. As can be seen from the figure, SL-g-PAA 3 For Co in water body 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ And Cd 2+ The ions have better adsorption capacity, wherein the ions have better adsorption capacity to Pb 2+ The adsorption amount of ions is the largest.
FIG. 4 is a graph showing the luminescence intensity and luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 7 of the present invention. From the figure, it can be seen that the concentration of the N- (4-aminobutyl) -N-ethyl isoluminol solution has a large influence on the luminous intensity of the resulting luminous hydrogel. With the increase of the concentration of the N- (4-aminobutyl) -N-ethyl isoluminol solution, the luminous intensity of the obtained luminous hydrogel is obviously enhanced.
FIG. 5 is a graph showing the luminescence intensity and luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 8 of the present invention. As can be seen from the figure, the concentration of the hydrogen peroxide solution has a large influence on the luminescence intensity of the resulting luminescent hydrogel. With the increase of the concentration of the hydrogen peroxide solution, the luminous intensity of the obtained luminous hydrogel is obviously enhanced. However, when the concentration of the hydrogen peroxide solution exceeds 0.1M, the increase in the concentration of the hydrogen peroxide solution causes rapid deterioration of the luminous intensity of the luminescent hydrogel, which is disadvantageous for continuous chemiluminescence for a long period of time.
FIG. 6 is a graph showing the luminescence intensity and luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 9 of the present invention. As can be seen from the graph, compared with the control group, the chemiluminescent intensity of all the luminescent hydrogels after heavy metal ions are adsorbed is obviously enhanced, which indicates that the existence of heavy metal ions in the hydrogel system can enhance the luminescent performance of the luminescent hydrogels. In addition, with Cu 2+ 、Ni 2+ 、Pb 2+ And Cd 2+ Ion compared with adsorption Co 2+ The luminous hydrogel after ions has obviously higher chemiluminescence intensity, and the luminous intensity can still be kept above 75% of the maximum value after 50 min.
FIG. 7 is a digital photograph of the lignin-based composite luminescent hydrogel prepared in example 10 of the present invention under dark conditions for different luminescent durations. As can be seen from the figure, the luminous intensity of the hydrogel gradually decreases as the luminous period increases. After 24 hours, the luminous intensity of the luminescent hydrogel was still visible to the naked eye. The result shows that the luminous hydrogel has the characteristics of high luminous intensity and long duration.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples. Accordingly, any other modifications, substitutions, and alterations herein without departing from the spirit and principles of this disclosure are intended to be within the scope of this disclosure.
Claims (4)
1. The application of the lignin-based composite hydrogel in luminescent materials is characterized in that the lignin-based composite hydrogel is lignin-based composite hydrogel after heavy metal ions are adsorbed, the lignin-based composite hydrogel after heavy metal ions are adsorbed is mixed with N- (4-aminobutyl) -N-ethyl isoluminol solution, and hydrogen peroxide solution is added after uniform stirring to obtain chemiluminescent hydrogel; the concentration of the N- (4-aminobutyl) -N-ethyl isoluminol solution is 1.0-25.0 mmol/L, the concentration of the hydrogen peroxide solution is 0.01-0.2 mol/L, and the ratio of the lignin-based composite hydrogel after heavy metal ions are adsorbed, the N- (4-aminobutyl) -N-ethyl isoluminol solution and the hydrogen peroxide solution is 0.1g:0.1 to 0.3mL: 0.1-0.3 mL;
the preparation method of the lignin-based composite hydrogel after heavy metal ions are adsorbed comprises the following steps: mixing the lignin-based composite hydrogel with a heavy metal ion aqueous solution, adsorbing for 10-30 hours in a shaking table at 20-40 ℃ and 50-150 rpm, and carrying out suction filtration after the adsorption is finished to obtain a solid sample, namely the lignin-based composite hydrogel after heavy metal ions are adsorbed; the heavy metal ion aqueous solution is one or more of cobalt chloride solution, cobalt nitrate solution, copper chloride solution, copper nitrate solution, nickel chloride solution, nickel nitrate solution, cadmium chloride solution, cadmium nitrate solution and lead nitrate solution; the concentration of the heavy metal ion aqueous solution is 10-400 mg/L; the ratio of the lignin-based composite hydrogel to the heavy metal ion aqueous solution is 0.1g: 50-100 mL;
the preparation method of the lignin-based composite hydrogel comprises the following steps:
1) Uniformly mixing sodium hydroxide aqueous solution and acrylic acid under the ice water bath condition, then sequentially adding lignin sulfonate, N-methylene bisacrylamide and potassium persulfate, and uniformly stirring;
2) And (3) carrying out free radical polymerization reaction on the mixed solution obtained in the step (1) under the ultrasonic auxiliary condition, soaking the obtained product in absolute ethyl alcohol overnight, and freeze-drying to obtain the lignin-based composite hydrogel.
2. The use according to claim 1, wherein in step 1), the concentration of the aqueous sodium hydroxide solution is 5 to 10mol/L, and the volume ratio of the aqueous sodium hydroxide solution to the acrylic acid is 1:1, a step of; the ratio of the acrylic acid, the lignosulfonate, the N, N-methylene bisacrylamide and the potassium persulfate is 3mL:0.1 to 1.5g:0.01 to 0.03g: 0.1-0.3 g; the lignosulfonate is sodium lignosulfonate.
3. The use according to claim 1, wherein in step 2) the free radical polymerization is carried out at a temperature of 40-80 ℃ for a time of 1-3 hours;
the freeze drying temperature is-50 to-60 ℃ and the time is 20 to 40 hours; the ultrasonic auxiliary conditions are as follows: 200-300W and 30-50 kHz.
4. The use according to claim 1, wherein the lignin-based composite hydrogel after adsorption of heavy metal ions is fully crushed, milled or mashed and then mixed with N- (4-aminobutyl) -N-ethyl isoluminol solution.
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