CN107376857B - Composite hydrogel material for adsorbing heavy metals and preparation method thereof - Google Patents
Composite hydrogel material for adsorbing heavy metals and preparation method thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920001661 Chitosan Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 14
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 13
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000011565 manganese chloride Substances 0.000 claims abstract description 13
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 13
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 42
- 238000003795 desorption Methods 0.000 abstract description 18
- 239000011133 lead Substances 0.000 abstract description 13
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910001430 chromium ion Inorganic materials 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 12
- 239000000499 gel Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002336 sorption--desorption measurement Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910052625 palygorskite Inorganic materials 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 210000005036 nerve Anatomy 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 208000007204 Brain death Diseases 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001605 fetal effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 231100000862 numbness Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 208000020016 psychiatric disease Diseases 0.000 description 1
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- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
-
- 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
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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 & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a composite hydrogel material for adsorbing heavy metals and a preparation method thereof. The material is prepared by respectively adding titanium tetrachloride and manganese chloride into acetic acid solution of chitosan, introducing nitrogen, heating in water bath to 55-70 ℃, adding an initiator, uniformly stirring, rapidly adding acrylamide, reacting at 60-65 ℃ for 1.5-3h, dehydrating, filtering and drying the product. The preparation method has simple process and short preparation time, and is suitable for large-scale production; meanwhile, the obtained inorganic-organic composite hydrogel doped with inorganic matters has good adsorption performance on lead, chromium and nickel ions, the adsorption capacity reaches 458.7mg/g, 318.2mg/g and 238.2mg/g respectively, and the inorganic-organic composite hydrogel still has high adsorption after being treated by a desorption agent and can be recycled.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a composite hydrogel material for adsorbing heavy metals in a water body and a preparation method thereof.
Background
Heavy metal means a density of greater than 4.5g/cm3The metal and heavy metal pollution is the pollution of waste water discharged by industries such as metallurgy, electroplating, tanning and the like to water and farmland soil environment. Heavy metals cannot be degraded by microorganisms and are easily absorbed by organisms and then enriched in higher organisms to generate cumulative poisoning. For example, heavy metal mercury can directly sink into the liver after entering a human body, and damage the brain vision nerves; heavy metal lead has high toxicity and causes damage to fetal nerve plates, resulting in brain death, senile dementia and other diseases; heavy metal chromium can cause numbness and mental disorder of limbs.
Although various treatment methods such as a conventional chemical precipitation method, a chelating flocculation method, a ferrite method, an ion exchange method, an evaporation concentration method, an adsorption method, a membrane separation method, an electrochemical method, and the like have been developed, the adsorption method has better practicability and wider application prospects because of wide application range, simple treatment process, wide raw material sources, lower cost, and better treatment effect compared with other treatment methods.
The research of the existing adsorbents mainly comprises activated carbon, agricultural wastes, resin, bentonite, fly ash, seaweed and the like, for example, application number 201710159372.2, namely organic-inorganic composite hydrogel for removing heavy metals in water, discloses that clay is firstly purified and activated and then compounded with organic matters to obtain composite hydrogel, and the method needs to treat the clay for multiple times, has complicated steps and consumes long time.
Application No. 201610851701.5 entitled "a method for preparing carboxymethyl chitosan/graphene oxide/polyacrylamide composite hydrogel" discloses that carboxymethyl chitosan is mixed with graphene oxide and propylamine enamide to react to obtain composite hydrogel, but the purpose of preparing the hydrogel is to make the hydrogel have good biocompatibility and mechanical properties, and the hydrogel can be used as materials of artificial skin, ligament and the like, and the document shows that the graphene oxide has the function of improving biocompatibility, and the carboxymethyl chitosan provides rigidity, so the hydrogel material does not show any adsorption effect on heavy metals from the functions and effects of the components of the application document.
Application No. 201610828084.7 preparation method of chitosan/palygorskite/polyacrylamide composite hydrogel discloses a method for preparing chitosan/palygorskite/polyacrylamide composite hydrogel by using chitosan, palygorskite and acrylamide as raw materials without adding initiator and N2Under the protection condition, the obtained composite hydrogel has obvious difference of adsorption amounts of different heavy metal ions, and the maximum saturated adsorption amount is less than 160 mg/g.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a composite hydrogel material which is short in preparation time and has high adsorption rate to various heavy metals and a preparation method thereof.
In order to achieve the object of the present invention, through a lot of experimental studies and diligent efforts, the following technical solutions are finally obtained: a preparation method of a composite hydrogel material for adsorbing heavy metals comprises the following steps: respectively adding titanium tetrachloride and manganese chloride into acetic acid solution of chitosan, introducing nitrogen, heating in a water bath to 55-70 ℃, adding an initiator, uniformly stirring, quickly adding acrylamide, reacting at 60-65 ℃ for 1.5-3h, dehydrating, filtering and drying a product to obtain a composite hydrogel material;
wherein the mass ratio of the titanium tetrachloride to the manganese chloride to the chitosan is (3-10): (0.2-0.8): 180, chitosan: the mass ratio of the acrylamide is 1 (65-90).
Further preferably, the preparation method of the composite hydrogel material for adsorbing heavy metals provided by the invention is characterized in that the mass ratio of the titanium tetrachloride to the manganese chloride to the chitosan is (5-7): (0.4-0.7): 180, chitosan: the mass ratio of acrylamide is 1: (73-82).
Further preferably, in the preparation method of the composite hydrogel material for adsorbing heavy metals, the amount of the initiator is 10-14% of the mass of the chitosan.
Further preferably, in the preparation method of the composite hydrogel material for adsorbing heavy metals provided by the invention, the initiator is potassium persulfate, ammonia persulfate or sodium persulfate, and the concentration of the initiator is 0.008-0.045 g/mL.
Further preferably, the preparation method of the composite hydrogel material for adsorbing heavy metals provided by the invention is characterized in that the mass concentration of the acetic acid solution of chitosan is 12-25 g/L.
Further preferably, the preparation method of the composite hydrogel material for adsorbing heavy metals provided by the invention is implemented, wherein the concentration of the acetic acid solution is 1-3%.
Further preferably, in the preparation method of the composite hydrogel material for adsorbing heavy metals provided by the invention, the viscosity average molecular weight of the chitosan is 250000-400000.
The dehydration and filtration of the product in the invention are all conventional technical means in the field, wherein the dehydration and filtration are generally carried out by absolute ethyl alcohol, the drying is generally carried out by an oven, and the drying temperature is 60-70 ℃.
Compared with the prior art, the invention has the following technical effects:
according to the invention, through a large number of experimental researches and screens, inorganic-organic composite hydrogel doped with inorganic matters is creatively obtained, compared with a single material, the gel adsorption capacity is improved, the gel has good adsorption performance on lead, chromium and nickel, the adsorption capacity reaches 458.7mg/g, 318.2mg/g and 238.2mg/g respectively, and the gel still has excellent heavy metal adsorption capacity after being treated by a desorption agent and can be recycled; the invention has simple process and short preparation time, and is suitable for large-scale production.
Detailed Description
The following further describes the embodiments of the present invention.
Example 1
Adding 0.3g of titanium tetrachloride and 0.03g of manganese chloride into 1.2L of an acetic acid solution of 15g/L of chitosan respectively (the viscosity average molecular weight of the chitosan is about 258000), wherein the concentration of the acetic acid solution is 1.5%, introducing nitrogen for 30min immediately after adding, heating the mixture in a water bath to 60 ℃, adding 90mL of potassium persulfate with the concentration of 0.02g/mL, stirring the mixture until the mixture is uniform, quickly adding 1180g of acrylamide, reacting in the water bath at 60 ℃ for 1.5h, adding absolute ethyl alcohol into the obtained product for dehydration and filtration, and drying the gel at 60 ℃ for 2h to obtain the composite hydrogel material.
Example 2
Adding 1g of titanium tetrachloride and 0.08g of manganese chloride into 0.9L of 20g/L acetic acid solution of chitosan (the viscosity average molecular weight of the chitosan is about 375000), wherein the concentration of the acetic acid solution is 3%, introducing nitrogen for 30min immediately after adding, heating in a water bath to 70 ℃, adding 63mL of ammonium persulfate solution with the concentration of 0.04g/mL, stirring the solution uniformly, quickly adding 1600g of acrylamide, reacting at 65 ℃ in the water bath for 1.5h, adding absolute ethyl alcohol into the obtained product for dehydration and filtration treatment, and drying the gel at 60 ℃ for 2h to obtain the composite hydrogel material.
Example 3
Adding 0.55g of titanium tetrachloride and 0.04g of manganese chloride into 0.9L of 20g/L chitosan acetic acid solution (the viscosity average molecular weight of chitosan is about 350000), wherein the concentration of the acetic acid solution is 3%, introducing nitrogen for 30min immediately after adding, heating in a water bath to 65 ℃, adding 73mL of ammonium persulfate solution with the concentration of 0.03g/mL, stirring the solution to be uniform, quickly adding 1350g of acrylamide, reacting for 1.5h at the temperature of 65 ℃ in the water bath, adding absolute ethyl alcohol into the obtained product for dehydration and filtration treatment, and drying the gel for 2h at the temperature of 60 ℃ to obtain the composite hydrogel material.
Example 4
Respectively adding 0.7g of titanium tetrachloride and 0.07g of manganese chloride into 1L of 18/L acetic acid solution of chitosan (the viscosity average molecular weight of the chitosan is about 320000), wherein the concentration of the acetic acid solution is 2%, immediately introducing nitrogen for 30min after adding, then heating in a water bath to 65 ℃, adding 80mL of ammonium persulfate solution with the concentration of 0.03g/mL, stirring the solution to be uniform, quickly adding 1450g of acrylamide, reacting in the water bath at 65 ℃ for 1.5h, adding absolute ethyl alcohol into the obtained product for dehydration and filtration treatment, and drying the gel at 60 ℃ for 2h to obtain the composite hydrogel material.
Example 5
Other conditions were the same as in example 1 except that the amounts of titanium tetrachloride added were changed to 0.2g, manganese chloride 0.01g and acrylamide 900g, to prepare a composite hydrogel material.
Example 6
Other conditions were the same as in example 1 except that the amounts of titanium tetrachloride added were changed to 1.2g, manganese chloride added to 1.0g and acrylamide added to 1800g, to prepare a composite hydrogel material.
Example 7
Effect experiment of adsorbing heavy metal ions:
1. treatment of ions containing divalent lead
20mg of the composite hydrogel obtained in examples 1 to 6 was taken to treat 25ml of a target treatment solution containing divalent lead ions, hydrochloric acid or sodium hydroxide was used to adjust the pH of the treatment solution to 4 to 5, the concentration of heavy metal lead ions was 500ppm, the temperature was 30 ℃, the shaking table speed was 200r/min, and after 2 hours, the concentration of heavy metal lead ions in the target treatment solution was measured to obtain the lead ion adsorption amount, and the results are shown in Table 1.
TABLE 1 lead ion adsorption amounts (mg/g) of composite hydrogels of examples 1 to 6
| Examples | 1 | 2 | 3 | 4 | 5 | 6 |
| Amount of adsorption | 458.7 | 472.1 | 511.4 | 491.2 | 387.6 | 402.3 |
Adsorption-desorption experiments:
taking the composite hydrogel for adsorbing divalent lead ions for the first time in example 1, using 0.5mol/L hydrochloric acid as a desorption agent, treating and adsorbing the composite hydrogel with 20ml of the desorption agent, detecting the concentration of heavy metal lead ions in the desorption agent after 1h, wherein the desorption rate is 93.2%, repeating the adsorption process of the composite hydrogel after desorption, and repeating the adsorption process for 3 times, wherein the adsorption amount of the composite hydrogel still reaches 415.8 mg/g.
The adsorption-desorption process of example was repeated using the first divalent lead ion-adsorbing composite hydrogel of example 5, and it was found that the adsorbed amount of the composite hydrogel was only 320.4mg/g after repeating 3 times.
Taking the repeated adsorption-desorption experiment of example 6, the adsorption amount of the composite hydrogel after repeating 3 times is only 332.5 mg/g.
2. Treatment of cadmium ions containing divalent ions
20mg of the composite hydrogel obtained in examples 1-6 was taken to treat 25ml of target treatment solution containing divalent cadmium ions, hydrochloric acid or sodium hydroxide was used to adjust the pH of the treatment solution to 4-5, the concentration of heavy metal cadmium ions was 500ppm, the temperature was 30 ℃, the shaking table speed was 200r/min, and after 2h, the concentration of heavy metal cadmium ions in the target treatment solution was measured to obtain the adsorption amount of cadmium ions, and the results are shown in Table 2.
TABLE 2 cadmium ion adsorption amounts (mg/g) of composite hydrogels of examples 1 to 6
| Examples | 1 | 2 | 3 | 4 | 5 | 6 |
| Amount of adsorption | 318.2 | 334.7 | 387.5 | 369.8 | 287.5 | 269.2 |
Adsorption-desorption experiments:
taking the composite hydrogel for adsorbing divalent cadmium ions for the first time in example 1, treating and adsorbing the composite hydrogel with 20ml of a desorption agent by using 0.3mol/L hydrochloric acid as the desorption agent, detecting the concentration of heavy metal cadmium ions in the desorption agent after 1 hour, wherein the desorption rate is 91.4%, repeating the adsorption process of the composite hydrogel after desorption, and repeating the adsorption process for 3 times, wherein the adsorption amount of the composite hydrogel still reaches 297.6 mg/g.
The adsorption-desorption process of example was repeated using the first adsorption divalent cadmium ion composite hydrogel of example 5, and it was found that the adsorption amount of the composite hydrogel was only 246.7mg/g after repeating 3 times.
Taking the repeated adsorption-desorption experiment of example 6, the adsorption amount of the composite hydrogel after repeating 3 times is only 231.5 mg/g.
3. Treatment of nickel ions containing two valences
20mg of the composite hydrogel obtained in examples 1-6 was taken to treat 25ml of a target treatment solution containing divalent nickel ions, hydrochloric acid or sodium hydroxide was used to adjust the pH of the treatment solution to 4-5, the concentration of heavy metal nickel ions was 500ppm, the temperature was 30 ℃, the shaking table speed was 200r/min, and after 2h, the concentration of heavy metal nickel ions in the target treatment solution was measured to obtain the nickel ion adsorption capacity, and the results are shown in Table 2.
TABLE 3 Nickel ion adsorption amounts (mg/g) of composite hydrogels of examples 1 to 6
| Examples | 1 | 2 | 3 | 4 | 5 | 6 |
| Amount of adsorption | 238.2 | 251.9 | 289.4 | 268.7 | 224.7 | 231.5 |
Adsorption-desorption experiments:
taking the composite hydrogel for adsorbing divalent nickel ions for the first time in example 1, treating and adsorbing the composite hydrogel with 20ml of a desorption agent by using 1.0mol/L hydrochloric acid as the desorption agent, detecting the concentration of heavy metal nickel ions in the desorption agent after 1 hour, wherein the desorption rate is 94.2%, repeating the adsorption process of the composite hydrogel after desorption, and repeating the adsorption process for 3 times, wherein the adsorption amount of the composite hydrogel still reaches 219.7 mg/g.
The adsorption-desorption process of example was repeated using the first divalent nickel ion-adsorbed composite hydrogel of example 5, and it was found that the adsorbed amount of the composite hydrogel was 205.2mg/g after repeating 3 times.
The adsorption-desorption experiment of example 6 was repeated 3 times, and the adsorption amount of the composite hydrogel was 216.8 mg/g.
Comparative example 1
Dissolving 0.3g of titanium tetrachloride (0.1738ml) in 15ml of absolute ethanol to obtain an alcoholic solution of titanium tetrachloride, adding 0.03g of manganese chloride, stirring for 15min under the condition of magnetic stirring in a water bath at 60 ℃, standing for 1h to obtain gel, drying the gel for 2h at 70 ℃ to obtain dry gel, and grinding the dry gel to obtain powder.
Comparative example 2
The xerogel powder obtained in comparative example 1 was calcined at 450 ℃ for 1 h.
Comparative example 3
Dissolving 18g of chitosan in 1.2L of acetic acid solution with the concentration of 1%, quickly adding 1180g of acrylamide, quickly and uniformly stirring, introducing nitrogen for 30min, adding 90mL of potassium persulfate with the concentration of 0.02g/mL under the protection of nitrogen, reacting for 1.5h under the condition of water bath at the temperature of 60 ℃, and cooling the reaction mixture after the reaction is finished.
Adjusting the cooled reaction mixture to be neutral by using 5% sodium hydroxide, pouring the neutral reaction mixture into 95% ethanol, carrying out suction filtration to obtain floccules, washing the floccules by using distilled water and absolute ethanol to obtain white solids, soaking the white solids in acetone for 24 hours, removing homopolymers in the mixture, carrying out suction filtration, washing precipitates by using 95% ethanol to remove a solvent, and drying the precipitates for 24 hours at 50 ℃ to obtain the chitosan and acrylamide graft copolymer.
Comparative example 4
Heavy metal ion adsorption experiments were carried out on the materials obtained in comparative examples 1 to 3 in accordance with the amount and procedure of example 7, and it was found that the adsorption amounts of divalent lead ions, divalent cadmium ions and divalent nickel ions of the manganese-doped titanium dioxide obtained in comparative examples 1 and 2 were extremely low, and were only less than 40mg/g, and the adsorption amounts of divalent lead ions, divalent cadmium ions and divalent nickel ions of the material obtained in comparative example 3 were 264.2mg/g, 189.1mg/g and 154.3mg/g, respectively, and that the adsorption and desorption processes were repeated three times for the adsorption material obtained in comparative example 3, and that the adsorption amounts of divalent lead ions, divalent cadmium ions and divalent nickel ions were 187.5mg/g, 121.2mg/g and 104.3mg/g, respectively.
Claims (4)
1. A preparation method of a composite hydrogel material for adsorbing heavy metals is characterized by comprising the following steps: respectively adding titanium tetrachloride and manganese chloride into acetic acid solution of chitosan, introducing nitrogen, heating in a water bath to 55-70 ℃, adding an initiator, uniformly stirring, quickly adding acrylamide, reacting at 60-65 ℃ for 1.5-3h, dehydrating, filtering and drying a product to obtain a composite hydrogel material; wherein the mass ratio of the titanium tetrachloride to the manganese chloride to the chitosan is (5-7): (0.4-0.7): 180, chitosan: the mass ratio of the acrylamide is 1 (73-82), and the viscosity average molecular weight of the chitosan is 250000-400000.
2. The method for preparing the composite hydrogel material for adsorbing heavy metal according to claim 1, wherein the amount of the initiator is 10-14% of the mass of the chitosan.
3. The method for preparing the composite hydrogel material for adsorbing heavy metal according to claim 1, wherein the initiator is potassium persulfate, ammonia persulfate or sodium persulfate, and the concentration of the initiator is 0.008-0.045 g/mL.
4. The preparation method of the composite hydrogel material for adsorbing heavy metal according to claim 1, wherein the concentration of the acetic acid solution of chitosan is 12-25 g/L.
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