CN113648982A - Preparation method of biomass-based hydrogel material capable of adsorbing heavy metal ions - Google Patents
Preparation method of biomass-based hydrogel material capable of adsorbing heavy metal ions Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000000017 hydrogel Substances 0.000 title claims abstract description 42
- 239000002028 Biomass Substances 0.000 title claims abstract description 35
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 29
- 150000002500 ions Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 230000010933 acylation Effects 0.000 claims abstract description 5
- 238000005917 acylation reaction Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical group Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 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 description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 3
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 25
- 239000003463 adsorbent Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- JACTUYDQIXZXHK-UHFFFAOYSA-N hydrazine;terephthalic acid Chemical compound NN.NN.OC(=O)C1=CC=C(C(O)=O)C=C1 JACTUYDQIXZXHK-UHFFFAOYSA-N 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a preparation method of a biomass-based hydrogel material capable of adsorbing heavy metal ions, wherein the biomass-based hydrogel material is sequentially reacted with a crosslinking agent, a carboxyl activating reagent and an acylation catalyst which are added in a deionized water solution state, and then is solidified and molded by a mold to prepare the biomass-based hydrogel material with a three-dimensional network structure. The invention takes renewable and biodegradable biomass-based materials as main raw materials, and has the advantages of wide sources, low cost, environmental friendliness and the like; the adsorbent has a three-dimensional network structure, and is strong in water absorption, large in specific surface area, multiple in adsorption sites and high in adsorption efficiency. The preparation method is simple, the steps are simple and convenient, the operability is strong, and the industrial application and popularization are easy.
Description
Technical Field
The invention relates to a preparation method of a biomass-based hydrogel material capable of adsorbing heavy metal ions, and belongs to the technical field of new materials.
Background
With increasing economic levels and frequent human activities, the content of heavy metal ions in sewage and wastewater produced by industrial, agricultural and mining activities as well as daily life is gradually increasing. The exceeding of heavy metal ions in the water body is extremely harmful, and the heavy metal ions are high in toxicity, non-degradable, easy to accumulate in underground water, even can cause biological accumulation through a food chain, and seriously threaten the ecological environment and human health. At present, methods for removing heavy metal ions in water mainly include a chemical flocculation method, an ion exchange method, a membrane filtration method, an electrolysis method, an adsorption method and the like. By integrating the removal capacity of heavy metal ions, the treatment energy consumption, the sensitivity of operating conditions, the possibility of secondary pollution after treatment and the like, the adsorption method adopting adsorbent treatment is more applied. However, most of the traditional adsorbents have certain limitations, such as low removal capacity when the activated carbon is used for treating low-concentration heavy metal wastewater, difficulty in meeting the recycling requirement and high cost; the nano particle adsorbent has small size, is difficult to perform subsequent solid-liquid separation and poses serious threat to human health; the adsorption capacity of the agricultural waste adsorbent is unstable, and the chemical oxygen demand in the water body is easily increased. In recent years, the hydrogel material has a wide application prospect in the field of heavy metal treatment in water due to the fact that the hydrogel material is rich in a large number of functional groups, large in specific surface area and good in adsorption performance.
The hydrogel is a three-dimensional network polymer formed by crosslinking through a physical or chemical method, and has the characteristics of water absorption and water insolubility due to the existence of a network structure and crosslinking of polymer chains. At present, the raw materials for preparing the hydrogel are more in variety, but most of the raw materials are polymerized by petrochemical raw materials. (reference 1, Wupeng Kangcheng Wangshen, research on adsorption of heavy metal ions by acrylic acid/acrylamide/sodium p-styrenesulfonate ternary copolymerized hydrogel, ion exchange and adsorption, 2020, 36 (04): 316-, the preparation of hydrogels from natural biomass-based materials is of increasing interest to researchers. Therefore, the development and preparation steps are simple and convenient, the production cost is low, the treatment efficiency is high, and the environment-friendly biomass-based hydrogel material is used for adsorbing heavy metal ions in water and strengthening the protection to the environment, and has very important significance.
Disclosure of Invention
The invention aims to provide a process method for efficiently and quickly preparing a biomass-based hydrogel material capable of adsorbing heavy metal ions.
The technical scheme adopted by the invention is as follows: a preparation method of a biomass-based hydrogel material capable of adsorbing heavy metal ions comprises the steps of reacting a biomass-based material with a crosslinking agent, a carboxyl activating reagent and an acylation catalyst which are added in sequence in a deionized water solution state, and then curing and forming the biomass-based hydrogel material through a mold to prepare the biomass-based hydrogel material with a three-dimensional network structure.
The preparation method of the biomass-based hydrogel material comprises the following specific processes:
(1) dissolving a biomass-based material in deionized water to prepare a deionized water solution with the mass concentration of 0.5-35%;
(2) adding a cross-linking agent into the deionized water solution obtained in the step (1), and fully stirring for 10-45 min to completely dissolve the cross-linking agent to obtain a uniform mixed solution A;
(3) dissolving a carboxyl activating reagent in deionized water, then dropwise adding the mixture into the mixed solution A obtained in the step (2), and fully stirring for 10-30 min to obtain a uniform mixed solution B;
(4) dissolving an acylation catalyst in deionized water, dropwise adding the solution into the mixed solution B obtained in the step (3), and fully stirring for 10-30 min to obtain a mixed solution C;
(5) and (5) pouring the mixed solution C obtained in the step (4) into a mould, sealing and standing at room temperature for 0.5-12 h, and then curing and forming to obtain the biomass-based hydrogel material.
The biomass-based material selected in the step (1) is one or a mixture of more of carboxymethyl cellulose, carboxylated starch, carboxymethyl chitosan and sodium alginate.
In the step (2), the cross-linking agent is one or a mixture of more of adipic dihydrazide, succinyl dihydrazide, terephthalic acid dihydrazide and hydrazine hydrate, and the using amount of the cross-linking agent accounts for 0.3-5.0% of the mass of the biomass-based material.
In the step (3), the carboxyl activating reagent is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and the using amount of the carboxyl activating reagent accounts for 0.6-8.0% of the mass of the biomass-based material.
In the step (4), the acyl catalyst is one or a mixture of more of N-hydroxysuccinimide, 1-hydroxy-benzotriazole and 1-hydroxy-7-azobenzotriazole, and the dosage of the acyl catalyst accounts for 0.5-6.5% of the mass of the biomass-based material.
The characteristics of the biomass-based hydrogel material prepared by the method are as follows: the product has good toughness and high strength, and is rich in functional groups such as carboxyl, hydroxyl and the like; the structure is loose and porous, the porosity is more than or equal to 40 percent, the internal pore diameter is 10-400 mu m, and the swelling ratio is more than or equal to 1500 percent. Can be used for adsorbing heavy metal ions in industrial, agricultural and domestic sewage, and is beneficial to environmental protection.
The invention has the following advantages:
(1) the hydrogel for adsorbing heavy metal ions is prepared by taking a renewable and biodegradable biomass-based material as a main body, has the advantages of wide raw material source, low cost, environmental friendliness and the like, and accords with the concept of green sustainable development.
(2) The prepared biomass-based hydrogel material has a three-dimensional network structure, strong water absorption, large specific surface area and a plurality of adsorption sites, and has a good adsorption effect on heavy metal ions in industrial and agricultural wastewater and domestic sewage.
(3) The preparation method is simple and convenient, has simple steps and strong operability, and is easy for industrial application and popularization.
Detailed Description
The present invention is further described below in conjunction with examples, which are to be understood as being illustrative only and in no way limiting.
Example 1:
2.4216 g of sodium carboxymethylcellulose is added into 150 ml of deionized water and is completely dissolved at room temperature; adding 0.0355 g of adipic dihydrazide into the sodium carboxymethylcellulose solution, and completely dissolving under the condition of magnetic stirring to obtain a mixed solution A1; dripping 4 ml of deionized water solution dissolved with 0.0491 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into the mixed solution A1, stirring for 15 min, and fully dissolving to obtain a mixed solution B1; 4 ml of deionized water solution containing 0.0237 g of N-hydroxysuccinimide is added dropwise into the mixed solution B1, and the mixture is magnetically stirred for 15 min at room temperature to be fully dissolved and is marked as mixed solution C1. And pouring the mixed solution C1 into a mould, sealing and standing at room temperature for 5 h to obtain the hydrogel material capable of adsorbing heavy metal ions. Taking 40 mg of the above absolutely dry hydrogel material, processing 25 ml of the above completely dry hydrogel material containing 50 mg/L of Cu2+、Pb2+、Cr6+The target treatment liquid of (4); adjusting the pH value of the target treatment solution to 3 by using nitric acid or sodium hydroxide, treating for 5 hours at the temperature of 25 ℃ and the shaking table speed of 100 r/min, and detecting the concentration of heavy metal copper ions in the target treatment solution to obtain Cu2+Adsorption rate of 91.4% and Pb2+The adsorption rate is 81.9 percent, and Cr6+The adsorption rate was 72.0%.
Example 2:
1.9811 g of sodium alginate is added into 150 ml of deionized water and is completely dissolved at room temperature; adding 0.0531 g of succinyl dihydrazide into the sodium alginate solution, and completely dissolving under the condition of magnetic stirring, wherein the label is mixed solution A2; dropwise adding 4 ml of deionized water in which 0.0873 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is dissolved into the mixed solution A2, stirring for 5 min, and fully dissolving to obtain a mixed solution B2; 4 ml of deionized water containing 0.0478 g of N-hydroxysuccinimide are added dropwise into the mixed solution B2, and the mixture is magnetically stirred at room temperature for 15 min and then fully dissolved, and the label is mixed solution C2. And pouring the mixed solution C2 into a mould, sealing and standing at room temperature for 4h to obtain the hydrogel material capable of adsorbing heavy metal ions. Taking 40 mg of absolutely dry hydrogel material, processing 25 ml of the absolutely dry hydrogel material to respectively contain 50 mg/L of Cu2+、Pb2+、Cr6+The target treatment liquid of (4); by using nitreAdjusting the pH of the treating solution to 3 with acid or sodium hydroxide at 25 deg.C and shaking table speed of 100 r/min, treating for 5 hr, and detecting the concentration of heavy metal copper ion in the target treating solution to obtain Cu2+Adsorption rate of 86.5% and Pb2+An adsorption rate of 79.3% and Cr6+The adsorption rate was 66.5%.
Example 3:
5.4352 g of carboxymethyl chitosan is added into 150 ml of deionized water and is completely dissolved at room temperature; 0.2321 g of terephthalic acid dihydrazine is added into the carboxymethyl chitosan solution and is completely dissolved under the condition of magnetic stirring, and the solution is marked as mixed solution A3; dropwise adding 4 ml of deionized water in which 0.3557 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is dissolved into the mixed solution A3, stirring for 10 min, and fully dissolving to obtain a mixed solution B3; 4 ml of deionized water in which 0.2517 g of 1-hydroxy-benzo-triazole is dissolved is dropwise added into the mixed solution B3, and the mixture is magnetically stirred for 30 min at room temperature to be fully dissolved and is marked as mixed solution C3. And pouring the mixed solution C3 into a mould, sealing and standing at room temperature for 8 h to obtain the hydrogel material capable of adsorbing heavy metal ions. Taking 40 mg of absolutely dry hydrogel material, processing 25 ml of the absolutely dry hydrogel material to respectively contain 50 mg/L of Cu2+、Pb2+、Cr6+The target treatment liquid of (4); adjusting the pH of the treating solution to 3 at 25 deg.C with nitric acid or sodium hydroxide at a shaker speed of 100 r/min, treating for 5 h, and detecting the concentration of heavy metal copper ions in the target treating solution to obtain Cu2+Adsorption rate of 90.3% and Pb2+The adsorption rate is 82.5 percent and the Cr content6 +The adsorption rate was 72.3%.
Example 4:
7.6542 g of carboxylated starch is added into 150 ml of deionized water and is completely dissolved at room temperature; adding 0.3215 g of hydrazine hydrate into the carboxylated starch solution, and completely dissolving under magnetic stirring to obtain mixed solution A4; dripping 4 ml of deionized water in which 0.5664 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is dissolved into the mixed solution A4, stirring for 25 min, and fully dissolving to obtain a mixed solution B4; dripping 4 ml of deionized water dissolved with 0.4538 g of 1-hydroxy-7-azobenzotriazole into the mixed solution B4, magnetically stirring for 30 min at room temperature for full dissolution, and markingAnd (6) mixing the solution C4. And pouring the mixed solution C4 into a mould, sealing and standing at room temperature for 10 h to obtain the hydrogel material capable of adsorbing heavy metal ions. Taking 40 mg of absolutely dry hydrogel material, processing 25 ml of the absolutely dry hydrogel material to respectively contain 50 mg/L of Cu2+、Pb2+、Cr6+The target treatment liquid of (4); adjusting the pH of the treating solution to 3 at 25 deg.C with nitric acid or sodium hydroxide at a shaker speed of 100 r/min, treating for 5 h, and detecting the concentration of heavy metal copper ions in the target treating solution to obtain Cu2+Adsorption rate of 93.4% and Pb2+The adsorption rate is 86.9 percent, and the Cr content6 +The adsorption rate was 68.1%.
Example 5:
5.4322 g of sodium alginate is added into 150 ml of deionized water and is completely dissolved at room temperature; 0.1901 g of adipic acid dihydrazide is added into the sodium alginate solution, and the solution is completely dissolved under the condition of magnetic stirring and is marked as mixed solution A5; dripping 4 ml of deionized water in which 0.2988 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is dissolved into the mixed solution A5, stirring for 25 min, and fully dissolving to obtain a mixed solution B5; 4 ml of deionized water containing 0.2444 g of N-hydroxysuccinimide are added dropwise to the mixture B5, and the mixture is magnetically stirred at room temperature for 30 min to be fully dissolved and is marked as a mixture C5. And pouring the mixed solution C5 into a mould, sealing and standing at room temperature for 12 h to obtain the hydrogel material capable of adsorbing heavy metal ions. Taking 40 mg of absolutely dry hydrogel material, processing 25 ml of the absolutely dry hydrogel material to respectively contain 50 mg/L of Cu2+、Pb2+、Cr6+The target treatment liquid of (4); adjusting the pH of the treating solution to 3 at 25 deg.C with nitric acid or sodium hydroxide at a shaker speed of 100 r/min, treating for 5 h, and detecting the concentration of heavy metal copper ions in the target treating solution to obtain Cu2+Adsorption rate of 95.7% and Pb2+The adsorption rate is 85.4 percent, and the Cr content6+The adsorption rate was 70.1%.
Claims (7)
1. A preparation method of a biomass-based hydrogel material capable of adsorbing heavy metal ions comprises the steps of reacting a biomass-based material with a crosslinking agent, a carboxyl activating reagent and an acylation catalyst which are added in sequence in a deionized water solution state, and then curing and forming the biomass-based hydrogel material through a mold to prepare the biomass-based hydrogel material with a three-dimensional network structure.
2. The method of claim 1, comprising the steps of:
(1) dissolving a biomass-based material in deionized water to prepare a deionized water solution with the mass concentration of 0.5-35%;
(2) adding a cross-linking agent into the deionized water solution obtained in the step (1), and fully stirring for 10-45 min to completely dissolve the cross-linking agent to obtain a uniform mixed solution A;
(3) dissolving a carboxyl activating reagent in deionized water, then dropwise adding the mixture into the mixed solution A obtained in the step (2), and fully stirring for 10-30 min to obtain a uniform mixed solution B;
(4) dissolving an acylation catalyst in deionized water, dropwise adding the solution into the mixed solution B obtained in the step (3), and fully stirring for 10-30 min to obtain a mixed solution C;
(5) and (5) pouring the mixed solution C obtained in the step (4) into a mould, sealing and standing at room temperature for 0.5-12 h, and then curing and forming to obtain the biomass-based hydrogel material.
3. The production method according to claim 1 or 2, characterized in that: the biomass-based material is one or a mixture of more of carboxymethyl cellulose, carboxylated starch, carboxymethyl chitosan and sodium alginate.
4. The method according to claim 1 or 2, characterized in that: the cross-linking agent is one or a mixture of more of adipic acid dihydrazide, succinyl dihydrazide, terephthalic acid dihydrazide and hydrazine hydrate, and the dosage of the cross-linking agent accounts for 0.3-5.0% of the mass of the biomass-based material.
5. The production method according to claim 1 or 2, characterized in that: the carboxyl activating reagent is 1-ethyl- (3-dimethyl aminopropyl) carbodiimide hydrochloride, and the using amount of the carboxyl activating reagent accounts for 0.6-8.0% of the mass of the biomass-based material.
6. The production method according to claim 1 or 2, characterized in that: the acyl catalyst is one or a mixture of more of N-hydroxysuccinimide, 1-hydroxy-benzotriazole and 1-hydroxy-7-azobenzotriazole, and the dosage of the acyl catalyst accounts for 0.5-6.5% of the mass of the biomass-based material.
7. The production method according to claim 1 or 2, characterized in that: the characteristics of the prepared biomass-based hydrogel material are as follows: the product has good toughness and high strength, and is rich in carboxyl and hydroxyl functional groups; has three-dimensional network structure, is loose and porous, has the porosity of more than or equal to 40 percent, the internal pore diameter of 10-400 mu m and the swelling ratio of more than or equal to 1500 percent.
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Application publication date: 20211116 |