CN113083258A - Preparation method of heavy metal-containing high-salinity wastewater recycling adsorbent - Google Patents
Preparation method of heavy metal-containing high-salinity wastewater recycling adsorbent Download PDFInfo
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- CN113083258A CN113083258A CN202110420935.5A CN202110420935A CN113083258A CN 113083258 A CN113083258 A CN 113083258A CN 202110420935 A CN202110420935 A CN 202110420935A CN 113083258 A CN113083258 A CN 113083258A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 64
- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- 239000003463 adsorbent Substances 0.000 title claims abstract description 50
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008346 aqueous phase Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000012071 phase Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 14
- 150000001879 copper Chemical class 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- -1 methylhydroxypropyl Chemical group 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 239000012528 membrane Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009388 chemical precipitation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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Images
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
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
Abstract
A preparation method of a heavy metal-containing high-salinity wastewater recycling adsorbent belongs to the field of high-salinity wastewater recycling and high-molecular adsorption materials. The invention comprises the following steps: s1, preparing adsorbent powder; s2, adding a dispersing agent and NaCl into deionized water, and stirring to obtain an aqueous phase solution A; s3, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, and adding adsorbent powder to obtain a mixture; s4, adding the aqueous phase solution A prepared in the step S2 into the mixture prepared in the step S3, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; after twice heating and reaction, cooling and washing, the heavy metal removing adsorbent is obtained. Solves the problems of high treatment cost, complex treatment process, low heavy metal removal rate, low adsorption capacity, narrow adsorption range, high adsorbent dissolution loss rate and the like of heavy metal-containing high-salt wastewater in the prior art.
Description
Technical Field
The invention relates to a technology in the field of heavy metal-containing high-salt wastewater recycling treatment and adsorption material preparation, and particularly relates to a preparation method of a heavy metal-containing high-salt wastewater recycling adsorbent.
Background
Water resources play an important role in national economic development and social production and are an indispensable part of people's life. However, with the rapid development of industry and agriculture, the discharge of a large amount of heavy metal-containing industrial salt-containing wastewater causes the water pollution to be increasingly serious. According to statistics, about 400 hundred million t of industrial wastewater is generated in China every year. Wherein the heavy metal wastewater accounts for about 60 percent. The waste water seriously pollutes surface water and underground water, so that the total amount of available water resources is sharply reduced. Heavy metal wastewater generally comes from industries such as mining, metal smelting and processing, electroplating, tanning, pesticides, papermaking, painting, printing and dyeing, nuclear technology, petrochemical industry and the like. And the salt content is higher than the requirement for water use, and the wastewater contains acid and heavy metal ions, and belongs to wastewater with high salt content. The heavy metals in the high-salinity wastewater are difficult to biodegrade, easy to be absorbed and enriched by organisms, and persistent in toxicity, so that the high-salinity wastewater is a pollutant with potential hazard, and if the pollution is not regulated, serious threats are caused to the ecological environment and human health. Therefore, how to effectively treat the heavy metal-containing high-salinity wastewater, protect the human health and the ecological environment, and relieve the pressure of water resources and environment in China is a problem which is not negligible at present.
At present, the treatment method for treating the heavy metal-containing high-salinity wastewater mainly comprises two methods: the first chemical method (including chemical precipitation, chemical reduction, electrochemical and high molecular heavy metal collector) is to remove heavy metal ions from high-salt waste water by chemical reaction. The chemical precipitation method is a water treatment method which is widely applied and mature in technology at present, is only suitable for treating high-concentration heavy metal salt-containing wastewater, and is easy to generate a large amount of sludge. The second physical method (including adsorption, solvent extraction, evaporation and solidification, ion exchange, and membrane separation) is a method of separating by adsorption and concentration without changing the chemical form of heavy metal ions. The membrane separation technology is a novel separation technology, can effectively purify waste water and recover some useful substances, and has the characteristics of energy conservation, no phase change, simple equipment, convenient operation and the like. The principle is that under the action of selective permeation of semipermeable membrane, the solute and solvent in the solution are separated under the drive of external energy, so as to attain the goal of separation and purification. However, the components of the industrial wastewater are complex, the treatment conditions are harsh, the separation performance and the service life of the membrane material are seriously influenced, and the application and popularization of the membrane material are restricted. The ion exchange resin method can selectively recover heavy metal in the high-salinity wastewater, the concentration of the heavy metal ions in the effluent water is far lower than that of the heavy metal ions in the water treated by the chemical precipitation method, and the amount of generated sludge is less. However, the ion exchange resin has the disadvantages of low mechanical strength, no temperature resistance and salt tolerance, low adsorption capacity, slow adsorption rate, difficult regeneration and the like.
Disclosure of Invention
The invention provides a heavy metal-containing high-salt wastewater recycling adsorbent and a preparation method thereof, aiming at the defects in the prior art, and solving the problems of high treatment cost, complex treatment process, low heavy metal removal rate, low adsorption capacity, narrow adsorption range, high adsorbent dissolution loss rate and the like of heavy metal-containing wastewater in the prior art.
The invention relates to a preparation method of a heavy metal-containing high-salinity wastewater recycling adsorbent, which comprises the following steps:
s1, weighing copper salt, manganese salt and iron salt according to a certain proportion, adding into 100mL deionized water, and stirring uniformly; then, 100mL of 2.5mol/L sodium hydroxide solution is added, and stirring is continued; and aging for 20h at 60 ℃; finally, filtering, washing, drying and roasting to obtain (Cu-Mn-Fe) adsorbent powder;
s2, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature to obtain an aqueous phase solution A;
s3, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, stirring at room temperature, and then adding (Cu-Mn-Fe) adsorbent powder into the mixture to obtain a mixture;
s4, adding the aqueous phase solution A prepared in the step S2 into the mixture prepared in the step S3, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 50-70 ℃ for reaction for 2-6h, then heating to 80-95 ℃ for reaction for 4-10 h; and finally, cooling and washing to obtain the (Cu-Mn-Fe) -loaded heavy metal removal adsorbent, which is marked as HP (Cu-Mn-Fe).
Preferably, the copper salt is at least one of copper sulfate, copper nitrate, copper chloride and copper acetate, the manganese salt is at least one of manganese sulfate, manganese nitrate, manganese chloride and manganese acetate, and the iron salt is at least one of ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate, ferric acetate and ferric acetylacetonate.
Preferably, the copper salt of the invention: manganese salt: the molar ratio of the iron salt is (1-2) to (1-3) to (2-5).
Preferably, the dispersant of the present invention is at least one of PEG-200, PEG-400, PEG-600, PEG-1000, hydroxymethyl cellulose, hydroxyethyl cellulose, and methylhydroxypropyl cellulose.
Preferably, the polymer monomer of the present invention is at least one of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate, and butyl methacrylate.
Preferably, the crosslinking agent of the present invention is at least one of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate, and allyl isocyanurate.
Preferably, the initiator of the present invention is benzoyl peroxide and/or azobisisobutyronitrile.
Preferably, the pore-foaming agent is at least one of toluene, isooctane, aviation gasoline and n-heptane.
Preferably, the weight ratio of the monomer and the cross-linking agent is 1:2-5:1, the weight ratio of the monomer and the cross-linking agent to the pore-forming agent is 3:1-1:0.5, and the addition amount of the initiator is 1.0-3.0% of the weight of the oil phase solution B.
A process for resource treatment of heavy metal-containing high-salt wastewater comprises the following steps: firstly, loading a heavy metal removal adsorbent HP (Cu-Mn-Fe) into a column, and utilizing the special chelation effect of rich special groups contained in the adsorbent on heavy metal ions in high-salt wastewater to ensure that the adsorbent has high adsorption capacity on the heavy metal ions in the high-salt wastewater, thereby realizing the resource treatment of the high-salt wastewater containing the heavy metals; then desorbing and regenerating the adsorbent by desorption liquid.
Technical effects
Compared with the prior art, the invention has the following technical effects:
hybridizing (Cu-Mn-Fe) powder into a pore channel of a high polymer material by an in-situ polymerization method to prepare a heavy metal removal adsorbent HP (Cu-Mn-Fe); then the heavy metal wastewater is filled into an adsorption column, and the resource treatment of the heavy metal wastewater (containing As, Pb, Cr, Cd, Cu, Ni, Co, Mn and the like) is realized through an adsorption-desorption process; solves the problems of high treatment cost, complex treatment process, low heavy metal removal rate, low adsorption capacity, narrow adsorption range, high adsorbent dissolution loss rate and the like of heavy metal-containing high-salt wastewater in the prior art.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the present invention.
FIG. 2 is a process diagram of the resource treatment of heavy metal-containing high-salinity wastewater.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description. The experimental procedures, in which specific conditions are not specified in the examples, were carried out according to the conventional methods and conditions.
Example 1
As shown in fig. 1, this example prepares an adsorbent for recycling treatment of heavy metal-containing high-salt wastewater according to the following method:
s1, weighing copper nitrate, manganese sulfate and ferric chloride according to the molar ratio of 1:2:4, adding the weighed copper nitrate, manganese sulfate and ferric chloride into 100mL of deionized water, and uniformly stirring; then, 100mL of 2.5mol/L sodium hydroxide solution is added, and stirring is continued; and aging for 20h at 60 ℃; finally, filtering, washing, drying and roasting to obtain (Cu-Mn-Fe) adsorbent powder;
s2, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature to obtain an aqueous phase solution A;
s3, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, stirring at room temperature, and then adding (Cu-Mn-Fe) adsorbent powder into the mixture to obtain a mixture;
s4, adding the aqueous phase solution A prepared in the step S2 into the mixture prepared in the step S3, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 60 ℃, reacting for 3 hours, then heating to 80 ℃, and reacting for 8 hours; and finally, cooling and washing to obtain the (Cu-Mn-Fe) -loaded heavy metal removal adsorbent which is marked as HP (Cu-Mn-Fe) -1.
Example 2
As shown in fig. 1, this example prepares an adsorbent for recycling treatment of heavy metal-containing high-salt wastewater according to the following method:
s1, weighing copper sulfate, manganese nitrate and ferric nitrate according to the molar ratio of 2:3:4, adding into 100mL of deionized water, and stirring uniformly; then, 100mL of 2.5mol/L sodium hydroxide solution is added, and stirring is continued; and aging for 20h at 60 ℃; finally, filtering, washing, drying and roasting to obtain (Cu-Mn-Fe) adsorbent powder;
s2, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature to obtain an aqueous phase solution A;
s3, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, stirring at room temperature, and then adding (Cu-Mn-Fe) adsorbent powder into the mixture to obtain a mixture;
s4, adding the aqueous phase solution A prepared in the step S2 into the mixture prepared in the step S3, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 60 ℃, reacting for 3 hours, then heating to 80 ℃, and reacting for 8 hours; and finally, cooling and washing to obtain the (Cu-Mn-Fe) -loaded heavy metal removal adsorbent, which is marked as HP (Cu-Mn-Fe) -2.
Example 3
As shown in fig. 1, this example prepares an adsorbent for recycling treatment of heavy metal-containing high-salt wastewater according to the following method:
s1, weighing copper salt, manganese salt and iron salt according to the molar ratio of 2:2:2, adding into 100mL of deionized water, and stirring uniformly; then, 100mL of 2.5mol/L sodium hydroxide solution is added, and stirring is continued; and aging for 20h at 60 ℃; finally, filtering, washing, drying and roasting to obtain (Cu-Mn-Fe) adsorbent powder;
s2, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature to obtain an aqueous phase solution A;
s3, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, stirring at room temperature, and then adding (Cu-Mn-Fe) adsorbent powder into the mixture to obtain a mixture;
s4, adding the aqueous phase solution A prepared in the step S2 into the mixture prepared in the step S3, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 60 ℃, reacting for 3 hours, then heating to 80 ℃, and reacting for 8 hours; and finally, cooling and washing to obtain the (Cu-Mn-Fe) -loaded heavy metal removal adsorbent, which is marked as HP (Cu-Mn-Fe) -3.
Example 4
As shown in fig. 1, this example prepares an adsorbent for recycling treatment of heavy metal-containing high-salt wastewater according to the following method:
s1, weighing copper acetate, manganese nitrate and ferrous sulfate according to the molar ratio of 1:3:5, adding the weighed copper acetate, manganese nitrate and ferrous sulfate into 100mL of deionized water, and uniformly stirring; then, 100mL of 2.5mol/L sodium hydroxide solution is added, and stirring is continued; and aging for 20h at 60 ℃; finally, filtering, washing, drying and roasting to obtain (Cu-Mn-Fe) adsorbent powder;
s2, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature to obtain an aqueous phase solution A;
s3, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, stirring at room temperature, and then adding (Cu-Mn-Fe) adsorbent powder into the mixture to obtain a mixture;
s4, adding the aqueous phase solution A prepared in the step S2 into the mixture prepared in the step S3, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 60 ℃, reacting for 3 hours, then heating to 80 ℃, and reacting for 8 hours; and finally, cooling and washing to obtain the (Cu-Mn-Fe) -loaded heavy metal removal adsorbent which is marked as HP (Cu-Mn-Fe) -4.
The treatment process of the heavy metal-removing adsorbent prepared in the examples 1 to 4 on the heavy metal-containing high-salt wastewater (the water quality condition is shown in the following table 1) is shown in fig. 2, and the adsorbent has high adsorption capacity on heavy metal ions in the high-salt wastewater by utilizing the special chelation effect of rich special groups contained in the adsorbent on the heavy metal ions in the high-salt wastewater, so that the resource treatment of the heavy metal-containing high-salt wastewater is realized. An adsorption process: firstly, filling a heavy metal removal adsorbent into a column, adsorbing 50BV of high-salt wastewater containing heavy metals, and recording the adsorbed effluent as effluent 1, effluent 2, effluent 3 and effluent 4 respectively; then desorbing and regenerating the catalyst by using a desorption agent.
The method adopts ICP to measure the content of each heavy metal ion in the high-salinity wastewater before and after adsorption, and calculates the removal rate of each heavy metal ion.
TABLE 1 summary of water quality before and after adsorption (unit: mg/L, Total Dissolved Solids (TDS) =51600 ppm)
Through the embodiment, the invention has the advantages that the adsorption capacity and the removal rate of heavy metal ions in the high-salinity wastewater are all about 90%, the content of the heavy metal ions in the effluent meets the solid salt recovery standard, and the high-salinity wastewater can be recycled.
It is to be emphasized that: the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a heavy metal-containing high-salinity wastewater recycling adsorbent is characterized by comprising the following steps:
s1, weighing copper salt, manganese salt and iron salt according to a certain molar ratio, adding into 100mL of deionized water, and stirring uniformly; then, 100mL of 2.5mol/L sodium hydroxide solution is added, and stirring is continued; and aging for 20h at 60 ℃; finally, filtering, washing, drying and roasting to obtain adsorbent powder;
s2, adding a dispersing agent and NaCl into deionized water, and stirring at room temperature to obtain an aqueous phase solution A;
s3, mixing a polymer monomer, a cross-linking agent and a pore-foaming agent according to a certain weight ratio to obtain an oil phase solution B, then adding an initiator, stirring at room temperature, and then adding adsorbent powder to obtain a mixture;
s4, adding the aqueous phase solution A prepared in the step S2 into the mixture prepared in the step S3, and stirring to disperse the oil phase into oil droplets with the particle size of 0.3-1.2mm in the aqueous phase; then heating to 50-70 ℃ for reaction for 2-6h, then heating to 80-95 ℃ for reaction for 4-10 h; and finally, cooling and washing to obtain the adsorbent for removing the heavy metals.
2. The method as claimed in claim 1, wherein the copper salt in step S1 is at least one of copper sulfate, copper nitrate, copper chloride and copper acetate; the manganese salt is at least one of manganese sulfate, manganese nitrate, manganese chloride and manganese acetate; the iron salt is at least one of ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate, ferric acetate and ferric acetylacetonate.
3. The preparation method of the heavy metal-containing high-salt wastewater recycling adsorbent according to claim 1, wherein the weight ratio of copper salt: manganese salt: the molar ratio of the iron salt is (1-2) to (1-3) to (2-5).
4. The method for preparing the heavy metal-containing high-salinity wastewater resource adsorbent of claim 1, wherein in step S2, the dispersant is at least one of PEG-200, PEG-400, PEG-600, PEG-1000, hydroxymethyl cellulose, hydroxyethyl cellulose, and methylhydroxypropyl cellulose.
5. The method as claimed in claim 1, wherein in step S3, the polymer monomer is at least one of methyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, propyl methacrylate, and butyl methacrylate.
6. The preparation method of the heavy metal-containing high-salinity wastewater recycling adsorbent as claimed in claim 1, characterized in that in the step S3, the cross-linking agent is at least one of divinylbenzene, allyl itaconate, diethylene glycol dimethacrylate, allyl methacrylate, and allyl isocyanurate.
7. The method for preparing the resource adsorbent for heavy metal-containing high-salt wastewater as claimed in claim 1, wherein in step S3, the initiator is benzoyl peroxide and/or azobisisobutyronitrile.
8. The method for preparing the heavy metal ion-containing high-salt wastewater resource adsorbent according to claim 1, wherein in the step S3, the pore-forming agent is at least one of toluene, isooctane, aviation gasoline and n-heptane.
9. The method for preparing the resource adsorbent for heavy metal-containing high-salt wastewater as claimed in claim 1, wherein in step S3, the weight ratio of the monomer to the cross-linking agent is 1:2-5:1, the weight ratio of the monomer to the cross-linking agent to the pore-forming agent is 3:1-1:0.5, and the addition amount of the initiator is 1.0-3.0% of the weight of the oil phase solution B.
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| CN114643039A (en) * | 2022-02-17 | 2022-06-21 | 广西大学 | Co used in manganese sulfate solution2+、Ni2+Preparation method and application of adsorbent |
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