CN113893832A - Preparation method and application of magnetic hectorite composite polymer dye adsorbent for treating dye wastewater - Google Patents
Preparation method and application of magnetic hectorite composite polymer dye adsorbent for treating dye wastewater Download PDFInfo
- Publication number
- CN113893832A CN113893832A CN202111293046.3A CN202111293046A CN113893832A CN 113893832 A CN113893832 A CN 113893832A CN 202111293046 A CN202111293046 A CN 202111293046A CN 113893832 A CN113893832 A CN 113893832A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- dye
- adsorbent
- hectorite
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 78
- 229920000642 polymer Polymers 0.000 title claims abstract description 73
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 title claims abstract description 70
- 229910000271 hectorite Inorganic materials 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000002351 wastewater Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 81
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 230000008929 regeneration Effects 0.000 claims abstract description 13
- 238000011069 regeneration method Methods 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 230000005415 magnetization Effects 0.000 claims abstract description 8
- 230000005408 paramagnetism Effects 0.000 claims abstract description 7
- 230000004043 responsiveness Effects 0.000 claims abstract description 7
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 150000001768 cations Chemical class 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical group C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- NSDSIQGBHACTLY-UHFFFAOYSA-N Reactive Blue 5 Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S(O)(=O)=O)C=C1NC(C=1)=CC=C(S(O)(=O)=O)C=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(O)(=O)=O)=C1 NSDSIQGBHACTLY-UHFFFAOYSA-N 0.000 claims description 11
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 claims description 10
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 9
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 9
- 229940012189 methyl orange Drugs 0.000 claims description 9
- KZMRYBLIGYQPPP-UHFFFAOYSA-O [4-[(2-chlorophenyl)-[4-[ethyl-[(3-sulfophenyl)methyl]amino]phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-ethyl-[(3-sulfophenyl)methyl]azanium Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S(O)(=O)=O)C=2C(=CC=CC=2)Cl)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 KZMRYBLIGYQPPP-UHFFFAOYSA-O 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000012966 redox initiator Substances 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 3
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- XHCCWBJFZUXJBV-UHFFFAOYSA-K trisodium 2-[(2-oxido-5-sulfophenyl)diazenyl]-3,6-disulfonaphthalene-1,8-diolate Chemical compound C1=CC(=C(C=C1S(=O)(=O)O)N=NC2=C(C3=C(C=C(C=C3C=C2S(=O)(=O)O)S(=O)(=O)O)[O-])[O-])[O-].[Na+].[Na+].[Na+] XHCCWBJFZUXJBV-UHFFFAOYSA-K 0.000 claims description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 claims 1
- 240000006413 Prunus persica var. persica Species 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 13
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- -1 polyethylene pyrrolidone Polymers 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 91
- 239000000499 gel Substances 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000006249 magnetic particle Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 8
- 229920002873 Polyethylenimine Polymers 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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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
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention relates to a preparation method and application of a magnetic hectorite composite polymer dye adsorbent for treating dye wastewater, wherein a modified chemical coprecipitation method is adopted to prepare magnetic nanoparticles, a silane coupling agent KH570 is adopted to modify the surfaces of the magnetic nanoparticles to obtain KH570 modified magnetic nanoparticles, and finally the KH570 modified magnetic nanoparticles, hectorite, polyethylene pyrrolidone and functional monomers are copolymerized to prepare the magnetic hectorite composite polymer dye adsorbent with an organic-inorganic double-network structure and a plurality of dye adsorption groups, the saturation magnetization is 3-14 emu/g, the remanence and the coercive force both tend to zero, the magnetic dye adsorbent has paramagnetism and magnetic responsiveness, the gel strength of a water-absorbing gel is 5-20 Pa.s, the dye adsorption capacity reaches 50-560 mg/g for a dye aqueous solution with the initial concentration of 100-1000 mg/L, the adsorption balance is achieved within 60-120 min, the adsorption capacity of the dye after 5 times of regeneration and cyclic utilization exceeds 90% of the first adsorption capacity, and the method can be widely applied to adsorption separation of dye wastewater, pollution control of dye wastewater and the like.
Description
Technical Field
The invention relates to a preparation method and application of a magnetic hectorite composite polymer dye adsorbent for treating dye wastewater.
Background
With the improvement of global industrialization degree, environmental pollution is getting worse, wherein water pollution seriously affects the production and life of people, and industrial wastewater is a main dye pollution source of water. The dye wastewater mainly comes from the dye and dye intermediate production industry and different industries such as textile, leather, papermaking, rubber, plastics, cosmetics, pharmacy, food and the like, has the characteristics of complex composition, large water quantity and water quality change, high chromaticity, high COD (chemical oxygen demand) and BOD (biochemical oxygen demand) concentration, more suspended matters, more substances difficult to biodegrade and the like, and is one of industrial wastewater difficult to treat. In addition, the dye wastewater not only has obvious chromaticity and influences the sense, but also contains toxic and harmful pollutants for water or human bodies, the ecological environment of the water can be damaged if the dye wastewater is directly discharged without treatment, and the toxic and harmful substances enter a food chain and influence the health of the human bodies. For a long time, the treatment of printing and dyeing wastewater is a worldwide problem. The existing methods for treating dye wastewater mainly comprise chemical, biological and physical methods and the like. The sedimentation flocculation method is simple to operate and low in cost, but the operation cost is increased by a large amount of generated sludge. The electrolysis method consumes a large amount of electricity and metal electrodes when treating wastewater. The photocatalytic oxidation has good effect only on low-concentration dye wastewater. The biological method has single selectivity and the microorganism is sensitive to the environment. The adsorption method has the advantages of mild adsorption conditions, good adaptability, easy operation, short treatment period, large adsorption capacity, high removal rate and the like, and is widely used for treating printing and dyeing wastewater. The adsorbent commonly used is active carbon, mineral, resin adsorbent, etc. The activated carbon has strong adsorption capacity and high removal rate, but has high cost, and is generally only used for the treatment or advanced treatment of printing and dyeing wastewater with lower concentration. The minerals include natural zeolite, bentonite, etc., and have good ion exchange capacity and adsorption performance, but low activity and difficult regeneration. The resin adsorbent has high treatment efficiency, can be regenerated under certain conditions, can still keep high efficiency after regeneration, and is suitable for treating dye wastewater. The traditional adsorbent can only be separated by traditional methods such as centrifugation, filtration and precipitation after adsorbing the dye, so that the time and labor are wasted, the energy is not saved, the environment is protected, the structure of the adsorbing material is easy to damage, the regeneration and the utilization of the adsorbing material are influenced, and the practical application of the adsorbing material is greatly limited.
In recent years, the development of nano materials and nano technology greatly promotes the progress of water treatment technology, and the magnetic nano material shows great application potential in the field of dye removal due to the advantages of high specific surface area, abundant active points, high magnetism and the like. Magnetic Fe3O4The nano adsorbent can adsorb dye pollutants in a water body, after adsorption is completed, the nano adsorbent is magnetically separated under the action of an external magnetic field, so that the adsorbent and the mother liquor are quickly and effectively separated, and the problems of difficult solid-liquid separation and difficult recovery and separation of the conventional adsorbent are well solved, however, the magnetic nano Fe3O4The particles also have some disadvantages which cannot be overcome by themselves, such as bare magnetic nano-Fe3O4The particles are unstable in air, are easy to be oxidized, are easy to corrode and agglomerate in an acid environment, and further lose the special properties of the nano material, so that the adsorption effect and the adsorption selectivity of the nano material are poor. To make Fe3O4The magnetic nano material can more effectively adsorb dye pollutants, must be protected and modified, and has active functional groups such as ammonia with strong chemical stability and strong dye adsorption on the surface thereofThe group, carboxyl, hydroxyl, sulfonic group and the like to reduce agglomeration and ensure that the dye has good dye adsorption, dispersibility, oxidation resistance and acid and alkali resistance, but the Fe is caused by the limitation of insufficient specific surface area and active functional groups3O4The dye adsorption capacity and the adsorption efficiency of the magnetic adsorbent need to be improved.
In order to further improve the adsorption capacity and stability of the magnetic adsorbent, a magnetic polymer nanocomposite adsorbent having both magnetic and polymer adsorbent functions is becoming a research hotspot of people. The polymer adsorbent contains more designable active adsorption groups, the functional groups of the polymer and the surfaces of the inorganic magnetic nanoparticles can generate physical and chemical actions, and the long-chain structure of the polymer reduces the agglomeration phenomenon of the inorganic nanoparticles, so that the dispersibility, stability and acid and alkali resistance of the magnetic nanoparticles are greatly improved. The preparation method of the magnetic polymer nano composite adsorbent mainly comprises an embedding method, a chemical conversion method, a monomer polymerization method and the like. The embedding method is to uniformly disperse the magnetic nanoparticles in a polymer solution, and then to coat the polymer on the surface of the magnetic nanoparticles by means of crosslinking, flocculation, atomization, dehydration and the like, or to form a hybrid of the polymer and the magnetic nanoparticles. The embedding method has the advantages of simple preparation and easy operation, but has the defects of immature control on the thickness of a macromolecular shell layer, incomplete coating, irregular shape, difficult mastering of the size and the like. The magnetic nano particles prepared by the chemical conversion method have uniform particle size distribution and easily controlled magnetic content, but have strict requirements on the preparation of the porous high molecular polymer, complex preparation process and difficultly controlled pore structure size and distribution. The monomer polymerization method comprises the steps of firstly dispersing the magnetic particles, the organic monomer, the initiator and other auxiliary agents uniformly by methods such as ultrasonic dispersion and the like, and then polymerizing according to different polymerization modes to prepare the magnetic polymer nano composite adsorbent, wherein the polymerization methods comprise suspension polymerization, dispersion polymerization, emulsion polymerization, microemulsion polymerization, miniemulsion polymerization, solution polymerization and the like. The magnetic polymer microsphere adsorbent with small particle size, uniform coating and controllable morphology can be prepared by adopting suspension polymerization, dispersion polymerization, emulsion polymerization, microemulsion polymerization and miniemulsion polymerization, but the post-treatment is complicated, a surfactant, a dispersing agent, a stabilizing agent and the like need to be removed, the magnetic content is not easy to be too high, otherwise the polymerization is unstable, deionized water is generally adopted as a solvent in the solution polymerization method, hydrophilic functional monomers are subjected to in-situ polymerization in the presence of magnetic nanoparticles to obtain the magnetic polymer nano composite adsorbent which is lightly crosslinked and can absorb water swelling, the method does not use an organic solvent, is environment-friendly, the magnetic content is easy to control, the dispersion uniformity of the magnetic nanoparticles is better, complicated post-treatment is not needed, and the process is simple, so that the magnetic polymer adsorbent prepared by adopting the aqueous solution polymerization method gradually draws attention of people, but the crosslinking agent adopted by the method is generally a chemical crosslinking agent, the crosslinking is not uniform, an uneven organic network structure is easy to form, the mechanical strength is insufficient, and the dye adsorption performance is influenced, so that the practical application of the dye is restricted.
Wen et al adopt 1, 2-dibromoethane cross-linked polyethyleneimine to synthesize polyethyleneimine nanogel, and then adopt an in-situ precipitation method to prepare magnetic polyethyleneimine nanocomposite hydrogel, wherein the removal rate of anionic dye CR exceeds 99%. Cheng et al synthesized magnetic polyvinyl alcohol/graphene oxide hydrogel by a one-step synthesis method, and the adsorption capacities of methylene blue and methyl violet were 231.12mg/g and 204.74mg/g, respectively. Shanehsaz et al prepared magnetic polypyrrole adsorbent by oxidative polymerization method, and active blue RB19 adsorption capacity reached 112.36 mg/g. The magnetic cellulose/polyacrylic acid hydrogel with carboxymethyl cellulose and polyacrylic acid as matrixes is prepared by Hosseina deh et al by a one-pot synthesis method, and the adsorption capacity of dye crystal violet reaches 189 mg/g. Beyki et al magnetic Fe with core-shell structure3O4And (3) taking cellulose as a matrix, adding epichlorohydrin and 1-methylimidazole to prepare the magnetic cellulose ionic liquid adsorbent, wherein the adsorption capacity of the Congo red dye reaches 131 mg/g. Luo et al convert gamma-Fe2O3And the cellulose and the activated carbon are crosslinked by using epoxy chloropropane to obtain the magnetic cellulose/activated carbon adsorbent, and the removal rate of methyl orange and methylene blue exceeds 99 percent. Chang et al covalently graft starch onto multi-layer carbon nanotubes, and then grow magnetic nanoparticles on the surface of the starch-grafted carbon nanotubes by using starch as a template to obtain a magnetic starch/carbon nanotube adsorbing material, AThe adsorption capacities of the orange and the methylene blue respectively reach 135.8mg/g and 94.1 mg/g. First, Pourjavadi et al synthesized magnetic Fe3O4@SiO2And (3) adding nano particles, and then adding starch and acrylic acid monomers to perform graft copolymerization to prepare the magnetic starch grafted polyacrylic acid hydrogel, wherein the removal rate of the crystal violet dye is close to 90%. Baldikova et al modify wheat straw with sodium citrate-sodium hydroxide, then prepare magnetic wheat straw adsorbent with acridine orange and methyl green adsorption capacities of 208.3mg/g and 384.6mg/g, respectively, by microwave synthesis. Xu and the like adopt a solvothermal method to synthesize amino modified magnetic nanoparticles, and then polyacrylic acid and the amino modified magnetic nanoparticles are added to carry out chemical grafting to prepare the magnetic polymer adsorbent, so that the adsorption rate of rhodamine R6G is high, and the adsorption capacity is 55.8 mg/g. Chen and the like adopt a solvothermal method to synthesize amino modified Fe3O4And adding crosslinking agents glutaraldehyde and polyethyleneimine into the nano particles to generate a magnetic polyethyleneimine adsorbent with a three-dimensional network structure, wherein the adsorption capacities of acid alizarin red, methyl orange, methylene blue, sunset yellow, nuclear fixation red and alizarin green are 145.7mg/g, 127.5mg/g, 137.0mg/g, 118.3mg/g and 126.8mg/g respectively.
The hectorite is a layered lithium magnesium silicate mineral material belonging to the sub-family of montmorillonite, and has a chemical structure formula of (Na, Li) X { (Mg)3-X,LiX)3[Si4O10](OH)2}·nH2And O. Like most silicate minerals, hectorite is a trioctahedral structure, i.e., the upper and lower silicon-oxygen tetrahedrons sandwich a layer of magnesium-oxygen octahedron to form a sheet and are stacked layer by layer in the vertical direction. Central Si4+、Mg2+Easily available and low-priced Li+The upper and lower surfaces of the trioctahedron are charged with negative charges through replacement, the negative charges are compensated by adsorbing some hydrated cations, the hectorite can be dispersed in water to form a sheet layer structural unit with the diameter of 20-30nm and the thickness of 1-4nm, the surface of a sheet layer is charged with negative electricity, the end surface of the sheet layer is charged with positive electricity, and the end surface of the separated sheet is attracted to the surface of another sheet to form the card palace-shaped three-dimensional physical network gel. The structural characteristics of the hectorite ensure that the hectorite has excellent adsorbability, ion exchange property, colloid dispersibility, suspension property and insertable layerThe modified product has wide application in chemical, building, biological, electronic and agricultural industries. Although many researches and reports on the hectorite composite polymer dye adsorbent at home and abroad are available, no related research report on the magnetic hectorite composite polymer dye adsorbent with an organic-inorganic double cross-linked structure exists at home and abroad.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a magnetic hectorite composite polymer dye adsorbent. Firstly, preparing magnetic nanoparticles by adopting an improved chemical coprecipitation method, then carrying out surface modification on the magnetic nanoparticles by adopting a silane coupling agent KH570 to obtain KH570 modified magnetic nanoparticles, and finally copolymerizing the KH570 modified magnetic nanoparticles, hectorite, polyvinylpyrrolidone and a functional monomer to prepare the magnetic hectorite composite polymer dye adsorbent with an organic-inorganic double-crosslinking structure and a plurality of dye adsorption groups. The compatibility of the inorganic nano hectorite and the polymer matrix is improved through the hydrogen bond action of the nano hectorite and the polymer matrix, and the adsorption performance of the dye and the gel strength of the water-absorbing gel are improved by utilizing the nano hectorite sheet with negative charges. The polyvinylpyrrolidone with the pyrrolidone dye adsorption group penetrates through the polymer three-dimensional network structure in a linear macromolecular structure, so that the elasticity and extensibility of the magnetic hectorite composite dye adsorbent network can be improved, and the adsorption of the magnetic hectorite composite dye adsorbent to dyes is facilitated. Through the graft copolymerization of the KH570 modified magnetic nanoparticles and the functional monomer, the compatibility of the magnetic nanoparticles and the polymer matrix is improved, the agglomeration of the magnetic nanoparticles is avoided, the macroscopic phase separation of the magnetic nanoparticles and the polymer matrix is inhibited, the magnetic intelligent separation of the magnetic polymer dye adsorption is realized, and the defects that the common adsorbent is difficult to separate solid from liquid and is easy to generate secondary pollution are well overcome.
According to the purpose of the invention, the preparation method of the magnetic hectorite composite polymer dye adsorbent is provided, and is characterized by comprising the following process steps:
A) FeCl is added3·6H2O、FeCl2·4H2O and deionized water are added toUniformly stirring in a three-neck flask, heating to 50-80 ℃ after nitrogen protection for 30min, then dropwise adding an ammonia water solution with the mass concentration of 25-30%, reacting at constant temperature for 3-6 h under nitrogen protection after the ammonia water solution is dropwise added, cooling to room temperature, washing for 3-5 times with deionized water, and separating with a magnet to obtain magnetic nanoparticles; FeCl3·6H2O、FeCl2·4H2O, an ammonia water solution with the mass concentration of 25-30% and deionized water in a mass ratio of 10-30: 5-10: 25-60: 100-200;
B) adding magnetic nanoparticles, a silane coupling agent KH570 and deionized water into a three-neck flask, uniformly stirring, heating to 50-80 ℃ after nitrogen protection for 30min, then dropwise adding an ammonia water solution with the mass concentration of 25-30%, reacting at constant temperature for 3-6 h under nitrogen protection, cooling to room temperature, washing with deionized water for 3-5 times, and separating magnets to obtain KH570 modified magnetic nanoparticles; the mass ratio of the magnetic nanoparticles to the silane coupling agent KH570 to the ammonia water solution with the mass concentration of 25-30% to the deionized water is (1-5: 2-15): 2-15: 100-200;
C) dissolving NaOH in 200mL of deionized water, slowly and dropwisely adding acrylic acid into a NaOH aqueous solution in an ice bath, and stirring to react for 0.5-2 h to obtain a partially neutralized acrylic acid aqueous solution; adding KH570 modified magnetic nanoparticles, acrylamide, hectorite, polyvinylpyrrolidone and a cross-linking agent into a partially neutralized acrylic acid aqueous solution, uniformly stirring, heating to 50-60 ℃, adding a redox initiator, initiating a polymerization reaction for 3-5 hours, finally washing a product with absolute ethyl alcohol for 3-5 times, magnetically separating, drying at 80 ℃, and crushing to obtain a magnetic hectorite composite polymer dye adsorbent; the molar ratio of acrylic acid to NaOH is 1: 0.5 to 0.8; the mass ratio of acrylic acid to acrylamide is 1-5: 1-5; the cross-linking agent accounts for 0.1-0.8% of the total mass of the acrylic acid and the acrylamide monomer; the redox initiator accounts for 0.1-2.0% of the total mass of the acrylic acid and the acrylamide monomer, and comprises an oxidant and a reducing agent, wherein the molar ratio of the oxidant to the reducing agent is (1-2): 1; the hectorite accounts for 5-20% of the total mass of the acrylic acid and the acrylamide monomers; the KH570 modified magnetic nanoparticles account for 5-30% of the total mass of acrylic acid and acrylamide monomers; the polyvinyl pyrrolidone accounts for 3-15% of the total mass of the acrylic acid and the acrylamide monomers;
D) the saturation magnetization of the magnetic hectorite composite polymer dye adsorbent is 3-14 emu/g, the remanence and the coercive force both tend to zero, the magnetic hectorite composite polymer dye adsorbent has paramagnetism and magnetic responsiveness, the gel strength of a water-absorbing gel is 5-20 Pa.s, the dye adsorption capacity reaches 50-560 mg/g for a dye aqueous solution with the initial concentration of 100-1000 mg/L, the adsorption balance is achieved within 60-120 min, and the dye adsorption capacity after 5 times of regeneration and cyclic utilization exceeds 90% of the first adsorption capacity.
The cross-linking agent used in the invention is selected from N, N' -methylene bisacrylamide, ethylene glycol diacrylate, monoethylene glycol diacrylate, diethylene glycol diacrylate, 1, 3-propylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, glycidyl methacrylate and polyethylene glycol diacrylate.
The oxidant used in the present invention is selected from ammonium persulfate, potassium persulfate and sodium persulfate, and the reducing agent is selected from sodium bisulfite, sodium sulfite, sodium thiosulfate and ferrous sulfate.
The dyes used according to the invention are selected from the group consisting of methylene blue, cationic blue FGL, cationic orange R, cationic bright yellow 7GL, cationic pink FG, methyl green, crystal violet, methyl orange, reactive black RB5, congo red, alizarin red, sunset yellow, alizarin green, acid chrome blue K and eosin Y.
The invention has the advantages and effects that:
1) the polymerization reaction is directly carried out in the aqueous solution, no environmental pollution is caused, the method is simple and easy to implement, and nitrogen protection is not required, so that a nitrogen device is omitted, and the investment cost of equipment is reduced.
2) Through the graft copolymerization of the KH570 modified magnetic nanoparticles and the functional monomer, the compatibility of the magnetic nanoparticles and the polymer matrix is improved, the agglomeration of the magnetic nanoparticles is avoided, the macroscopic phase separation of the magnetic nanoparticles and the polymer matrix is inhibited, the magnetic intelligent separation of the magnetic polymer dye adsorption is realized, and the defects that the common adsorbent is difficult to separate solid from liquid and is easy to generate secondary pollution are well overcome.
3) The KH570 modified magnetic nanoparticles, the hectorite and the functional monomer are copolymerized to prepare the magnetic polymer dye adsorbent with an organic-inorganic double-crosslinking structure and multiple dye adsorption groups, and the adsorption performance of the magnetic polymer dye adsorbent is further improved through the synergistic effect of the multiple adsorption groups;
4) the compatibility of the inorganic nano hectorite and the polymer matrix is improved through the hydrogen bond action of the nano hectorite and the polymer matrix, and the adsorption performance of the dye and the gel strength of the water-absorbing gel are improved by utilizing the nano hectorite sheet with negative charges.
5) The polyvinylpyrrolidone with the pyrrolidone dye adsorption group penetrates through the polymer three-dimensional network structure in a linear macromolecular structure, so that the elasticity and extensibility of the magnetic hectorite composite dye adsorbent network can be improved, and the adsorption of the magnetic hectorite composite dye adsorbent to dyes is facilitated.
The magnetic hectorite composite polymer dye adsorbent provided by the invention has the following measurement methods of hysteresis performance, dye adsorption rate, adsorption capacity, regeneration and recycling performance and gel strength of water-absorbing gel.
The magnetic hysteresis performance of the magnetic hectorite composite polymer dye adsorbent was determined using a model LDJ-9600 vibrating magnetometer (VSM).
Putting a dye aqueous solution with the concentration of 100-1000 mg/L and 0.2g of dried and ground magnetic hectorite composite polymer dye adsorbent into a 250mL conical flask, then putting the conical flask into an oscillator for oscillation adsorption, sampling after oscillating for a certain time, measuring the absorbance of a sample at the maximum absorption wavelength of the dye by using a spectrophotometer, measuring 3 times for each sample, taking an average value, and taking the dye adsorption quantityq t And adsorption capacityq eRespectively calculated according to the following formula:
q t (mg/g)={(C 0- C t)V}/m (1)
q e (mg/g)={(C 0- C e)V}/m (2)
whereinC 0、C tAnd, andC erespectively is the initial concentration of the dye, the concentration of the dye in a certain time of oscillation adsorption and the equilibrium concentration of dye adsorption (mg.L-1),Vthe volume of the solution (L) is,mthe mass (g) of the magnetic hectorite composite polymer dye adsorbent.
And (3) vibrating and desorbing the magnetic hectorite composite polymer dye adsorbent saturated with adsorbed dye by using 50mL of 0.5 mol/L hydrochloric acid solution, and measuring the concentration of the dye in the solution by using a spectrophotometer after desorbing for a certain time until the desorption balance is reached. And drying and crushing the desorbed magnetic hectorite composite polymer dye adsorbent, adsorbing the dye again under the same condition, measuring the dye adsorption capacity of the magnetic hectorite composite polymer dye adsorbent by using a spectrophotometer, comparing the dye adsorption capacity with the adsorption capacity of the dye for the first time, and repeatedly performing regeneration cycle adsorption for 5 times to evaluate the regeneration cycle utilization performance of the magnetic hectorite composite polymer dye adsorbent.
Accurately weighing about 0.1g of dried and crushed magnetic hectorite composite polymer dye adsorbent, putting the magnetic hectorite composite polymer dye adsorbent into a 250mL beaker, then adding 100mL of distilled water, fully absorbing water at room temperature, filtering unadsorbed water by using a 100-mesh stainless steel screen until the gel reaches water absorption balance until no water drops, and then measuring the apparent viscosity of the water-absorbing gel by using a rotational viscometer, namely the gel strength of the water-absorbing gel of the magnetic hectorite composite polymer dye adsorbent.
Fourth, detailed description of the invention
For better understanding of the present invention, the following examples are given to further illustrate the present invention, but the present invention is not limited to the following examples.
Example 1:
adding 10g of FeCl3·6H2O and 5gFeCl2·4H2Adding O and 100mL of deionized water into a three-neck flask, uniformly stirring, raising the temperature to 80 ℃ after nitrogen protection for 30min, then dropwise adding 25g of ammonia water solution with the mass concentration of 25-30%, and after dropwise adding of the ammonia water solution, carrying out nitrogen protection constant-temperature reactionCooling to room temperature for 3h, washing for 4 times by using deionized water, and carrying out magnet separation to obtain magnetic nanoparticles; adding 3g of magnetic nanoparticles, 8g of silane coupling agent KH570 and 150mL of deionized water into a three-neck flask, uniformly stirring, heating to 80 ℃ after nitrogen protection for 30min, then dropwise adding 10g of ammonia water solution with the mass concentration of 25-30%, cooling to room temperature after nitrogen protection and constant-temperature reaction for 3h, washing with deionized water for 3 times, and carrying out magnet separation to obtain the KH570 modified magnetic nanoparticles.
Dissolving 5.4g of NaOH in 200mL of deionized water, slowly and dropwisely adding 16g of acrylic acid into an aqueous solution of NaOH in an ice bath, and stirring for reacting for 1h to obtain a partially neutralized acrylic acid aqueous solution; adding 8g of KH570 modified nano magnetic particles, 24g of acrylamide, 4.8g of hectorite, 4g of polyvinylpyrrolidone and 0.10g of ethylene glycol diacrylate into a part of neutralized acrylic acid aqueous solution, uniformly stirring, heating to 50 ℃, adding 0.54g of potassium persulfate and 0.18g of sodium thiosulfate, initiating a polymerization reaction for 5 hours, finally washing a product with absolute ethyl alcohol for 3 times, carrying out magnetic separation, drying at 80 ℃, and crushing to obtain a magnetic hectorite composite polymer dye adsorbent, wherein the saturation magnetization is 9.5emu/g, the coercive force and the coercive force both tend to zero, the magnetic hectorite composite polymer dye adsorbent has paramagnetism and magnetic responsiveness, and the gel strength of a water-absorbing gel is 18 Pa.s; for the crystal violet, methylene blue, sunset yellow and alizarin green aqueous solution with the initial concentration of 600mg/L, the adsorption capacities of the magnetic hectorite composite polymer dye adsorbent for the crystal violet, the methylene blue, the sunset yellow and the alizarin green respectively reach 325mg/g, 273mg/g, 181mg/g and 138mg/g, the adsorption balance is reached in 90min, and the adsorption capacities of the crystal violet, the methylene blue, the sunset yellow and the alizarin green after 5 times of recycling are all more than 90% of the first adsorption capacity.
Example 2:
15g of FeCl3·6H2O and 6gFeCl2·4H2Adding O and 150mL of deionized water into a three-neck flask, uniformly stirring, heating to 50 ℃ after nitrogen protection for 30min, then dropwise adding 35g of an ammonia water solution with the mass concentration of 25-30%, after dropwise adding of the ammonia water solution, carrying out nitrogen protection constant-temperature reaction for 6h, cooling to room temperature, washing with deionized water for 5 times, and carrying out magnet separation to obtain magnetic nanoparticles; 2.5g of magnetic nanoparticles,Adding 5g of a silane coupling agent KH570 and 100mL of deionized water into a three-neck flask, uniformly stirring, heating to 50 ℃ after nitrogen protection for 30min, then dropwise adding 6g of an ammonia water solution with the mass concentration of 25-30%, reacting at constant temperature under nitrogen protection for 6h, cooling to room temperature, washing with deionized water for 5 times, and carrying out magnet separation to obtain the KH570 modified nano magnetic particles.
Dissolving 9g of NaOH in 200mL of deionized water, slowly dropwise adding 24g of acrylic acid into the NaOH aqueous solution in ice bath, and stirring for reaction for 2 hours to obtain a partially neutralized acrylic acid aqueous solution; adding 2g of KH570 modified nano magnetic particles, 16g of acrylamide, 2g of hectorite, 6g of polyvinylpyrrolidone and 0.16g of diethylene glycol diacrylate into a part of neutralized acrylic acid aqueous solution, uniformly stirring, heating to 50 ℃, adding 0.60g of potassium persulfate and 0.20g of sodium sulfite to initiate polymerization reaction for 5 hours, finally washing the product with absolute ethyl alcohol for 5 times, magnetically separating, drying at 80 ℃, and crushing to obtain the magnetic hectorite composite polymer dye adsorbent, wherein the saturation magnetization is 3emu/g, the remanence and the coercive force both tend to zero, and the magnetic hectorite composite polymer dye adsorbent has paramagnetism and magnetic responsiveness, and the gel strength of a water-absorbing gel is 5 Pa.s; for the cation bright yellow 7GL, the active black RB5, the alizarin red and the sunset yellow aqueous solution with the initial concentration of 800mg/L, the adsorption capacities of the cation bright yellow 7GL, the active black RB5, the alizarin red and the sunset yellow of the magnetic hectorite composite polymer dye adsorbent respectively reach 453mg/g, 315mg/g, 272mg/g and 211mg/g, the adsorption balance is reached in 60min, and the adsorption capacities of the cation bright yellow 7GL, the active black RB5, the alizarin red and the sunset yellow after 5 times of regeneration cycle utilization all exceed 90% of the first adsorption capacity.
Example 3:
20g of FeCl36H2O and 8gFeCl2·4H2Adding O and 200mL of deionized water into a three-neck flask, uniformly stirring, heating to 70 ℃ after nitrogen protection for 30min, then dropwise adding 50g of an ammonia water solution with the mass concentration of 25-30%, after dropwise adding of the ammonia water solution, carrying out nitrogen protection constant-temperature reaction for 4h, cooling to room temperature, washing with deionized water for 4 times, and carrying out magnet separation to obtain magnetic nanoparticles; adding 4g of magnetic nanoparticles, 12g of silane coupling agent KH570 and 200mL of deionized water into a three-neck flask, uniformly stirring, and raising the temperature after 30min under the protection of nitrogenAnd (3) heating to 80 ℃, then dropwise adding 12g of 25-30% ammonia water solution, reacting at constant temperature under the protection of nitrogen for 3 hours, cooling to room temperature, washing for 3 times by using deionized water, and carrying out magnet separation to obtain the KH570 modified nano magnetic particles.
Dissolving 8g of NaOH in 200mL of deionized water, slowly dropwise adding 24g of acrylic acid into the NaOH aqueous solution in ice bath, and stirring for reaction for 2 hours to obtain a partially neutralized acrylic acid aqueous solution; adding 4g of KH570 modified nano magnetic particles, 18g of acrylamide, 4g of hectorite, 4.8g of polyvinylpyrrolidone and 0.10g of monoethylene glycol diacrylate into a part of neutralized acrylic acid aqueous solution, uniformly stirring, heating to 50 ℃, adding 0.62g of ammonium persulfate and 0.21g of sodium bisulfite, initiating a polymerization reaction for 5 hours, finally washing a product with absolute ethyl alcohol for 3 times, carrying out magnetic separation, drying at 80 ℃, and crushing to obtain a magnetic hectorite composite polymer dye adsorbent, wherein the saturation magnetization is 5.1emu/g, the coercive force and the coercive force both tend to zero, and the magnetic adsorbent has paramagnetism and magnetic responsiveness, and the gel strength of a water-absorbing gel is 12 Pa.s; for the crystal violet, cation bright yellow 7GL, active black RB5 and methyl orange aqueous solution with the initial concentration of 1000mg/L, the adsorption capacities of the magnetic hectorite composite polymer dye adsorbent, namely the crystal violet, the cation bright yellow 7GL, the active black RB5 and the methyl orange respectively reach 560mg/g, 502mg/g, 456mg/g and 401mg/g, 70min reaches adsorption balance, and the adsorption capacities of the crystal violet, the cation bright yellow 7GL, the active black RB5 and the methyl orange after 5 times of regeneration cyclic utilization all exceed 90% of the first adsorption capacity.
Example 4:
30g of FeCl3·6H2O and 10gFeCl2·4H2Adding O and 200mL of deionized water into a three-neck flask, uniformly stirring, heating to 70 ℃ after nitrogen protection for 30min, then dropwise adding 60g of an ammonia water solution with the mass concentration of 25-30%, after dropwise adding of the ammonia water solution, carrying out nitrogen protection constant-temperature reaction for 4h, cooling to room temperature, washing with deionized water for 5 times, and carrying out magnet separation to obtain magnetic nanoparticles; adding 5g of magnetic nanoparticles, 15g of silane coupling agent KH570 and 200mL of deionized water into a three-neck flask, uniformly stirring, raising the temperature to 70 ℃ after 30min of nitrogen protection, then dropwise adding 15g of ammonia water solution with the mass concentration of 25-30%, and keeping constant under the nitrogen protectionAnd (3) reacting at a high temperature for 4 hours, cooling to room temperature, washing with deionized water for about 5 times, and carrying out magnet separation to obtain the KH570 modified nano magnetic particles.
Dissolving 7.2g of NaOH in 200mL of deionized water, slowly and dropwisely adding 20g of acrylic acid into the NaOH aqueous solution in ice bath, and stirring for reacting for 0.5h to obtain a partially neutralized acrylic acid aqueous solution; adding 6g of KH570 modified nano magnetic particles, 20g of acrylamide, 3g of hectorite, 3.6g of polyvinylpyrrolidone and 0.08g of 1, 3-propylene glycol diacrylate into a part of neutralized acrylic acid aqueous solution, uniformly stirring, heating to 60 ℃, adding 0.36g of sodium persulfate and 0.12g of sodium bisulfite to initiate a polymerization reaction for 3 hours, finally washing a product with absolute ethyl alcohol for 5 times, magnetically separating, drying at 80 ℃, and crushing to obtain a magnetic hectorite composite polymer dye adsorbent, wherein the saturation magnetization is 7.8emu/g, the residual magnetism and the coercive force both tend to zero, and the magnetic hectorite composite polymer dye adsorbent has paramagnetism and magnetic responsiveness, and the gel strength of a water-absorbing gel is 15 Pa.s; for the aqueous solution of methylene blue, methyl green, active black RB5 and alizarin red with the initial concentration of 300mg/L, the adsorption capacities of the magnetic hectorite composite polymer dye adsorbents of the methylene blue, the methyl green, the active black RB5 and the alizarin red respectively reach 170mg/g, 150mg/g, 136mg/g and 120mg/g, 105min reaches adsorption balance, and the adsorption capacities of the methylene blue, the methyl green, the active black RB5 and the alizarin red after 5 times of regeneration cyclic utilization all exceed 90% of the first adsorption capacity.
Example 5:
19.6g of FeCl3·6H2O and 7.2g FeCl2·4H2Adding O and 150mL of deionized water into a three-neck flask, uniformly stirring, heating to 60 ℃ after nitrogen protection for 30min, then dropwise adding 50g of an ammonia water solution with the mass concentration of 25-30%, after dropwise adding of the ammonia water solution, carrying out nitrogen protection constant-temperature reaction for 5h, cooling to room temperature, washing with deionized water for 3 times, and carrying out magnet separation to obtain magnetic nanoparticles; adding 1g of magnetic nanoparticles, 2g of silane coupling agent KH570 and 100mL of deionized water into a three-neck flask, uniformly stirring, heating to 60 ℃ after nitrogen protection for 30min, then dropwise adding 2g of ammonia water solution with the mass concentration of 25-30%, cooling to room temperature after nitrogen protection and constant-temperature reaction for 5h, washing with deionized water for 5 times, and carrying out magnet separation to obtain KH570 modified nanoparticlesMagnetic particles.
Dissolving 9g of NaOH in 200mL of deionized water, slowly dropwise adding 24g of acrylic acid into the NaOH aqueous solution in ice bath, and stirring for reaction for 2 hours to obtain a partially neutralized acrylic acid aqueous solution; adding 12g of KH570 modified nano magnetic particles, 16g of acrylamide, 8g of hectorite, 1.2g of polyvinylpyrrolidone and 0.12g N, N' -methylene bisacrylamide into a part of neutralized acrylic acid aqueous solution, uniformly stirring, heating to 60 ℃, adding 0.48g of ammonium persulfate and 0.16g of sodium bisulfite, initiating a polymerization reaction for 3 hours, finally washing a product with absolute ethyl alcohol for 3 times, carrying out magnetic separation, drying at 80 ℃, and crushing to obtain a magnetic hectorite composite polymer dye adsorbent, wherein the saturation magnetization is 14emu/g, the coercive force and the coercive force both tend to zero, and the magnetic and magnetic responsivity are realized, and the gel strength of a water-absorbing gel is 20 Pa.s; for the water solution of crystal violet, cation bright yellow 7GL, sunset yellow and alizarin green with the initial concentration of 100mg/L, the adsorption capacities of the magnetic polymer dye adsorbents of crystal violet, cation bright yellow 7GL, methyl orange and alizarin green respectively reach 90mg/g, 81mg/g, 69mg/g and 50mg/g, the adsorption balance is reached within 120min, and the adsorption capacities of the crystal violet, cation bright yellow 7GL, methyl orange and Congo red after 5 times of regeneration and cyclic utilization all exceed 90% of the first adsorption capacity.
Claims (4)
1. A preparation method and application of a magnetic hectorite composite polymer dye adsorbent for treating dye wastewater are characterized by comprising the following process steps:
A) FeCl is added3·6H2O、FeCl2·4H2Adding O and deionized water into a three-neck flask, stirring uniformly, heating to 50-80 ℃ after nitrogen protection for 30min, then dropwise adding an ammonia water solution with the mass concentration of 25-30%, after dropwise adding the ammonia water solution, carrying out nitrogen protection constant-temperature reaction for 3-6 h, cooling to room temperature, washing with deionized water for 3-5 times, and carrying out magnet separation to obtain magnetic nanoparticles; FeCl3·6H2O、FeCl2·4H2O, an ammonia water solution with the mass concentration of 25-30% and deionized water in a mass ratio of 10-30: 5-10: 25-60: 100-200;
B) adding magnetic nanoparticles, a silane coupling agent KH570 and deionized water into a three-neck flask, uniformly stirring, heating to 50-80 ℃ after nitrogen protection for 30min, then dropwise adding an ammonia water solution with the mass concentration of 25-30%, reacting at constant temperature for 3-6 h under nitrogen protection, cooling to room temperature, washing with deionized water for 3-5 times, and separating magnets to obtain KH570 modified magnetic nanoparticles; the mass ratio of the magnetic nanoparticles to the silane coupling agent KH570 to the ammonia water solution with the mass concentration of 25-30% to the deionized water is (1-5: 2-15): 2-15: 100-200;
C) dissolving NaOH in 200mL of deionized water, slowly and dropwisely adding acrylic acid into a NaOH aqueous solution in an ice bath, and stirring to react for 0.5-2 h to obtain a partially neutralized acrylic acid aqueous solution; adding KH570 modified magnetic nanoparticles, acrylamide, hectorite, polyvinylpyrrolidone and a cross-linking agent into a partially neutralized acrylic acid aqueous solution, uniformly stirring, heating to 50-60 ℃, adding a redox initiator, initiating a polymerization reaction for 3-5 hours, finally washing a product with absolute ethyl alcohol for 3-5 times, magnetically separating, drying at 80 ℃, and crushing to obtain a magnetic hectorite composite polymer heavy metal ion adsorbent; the molar ratio of acrylic acid to NaOH is 1: 0.5 to 0.8; the mass ratio of acrylic acid to acrylamide is 1-5: 1-5; the cross-linking agent accounts for 0.1-0.8% of the total mass of the acrylic acid and the acrylamide monomer; the redox initiator accounts for 0.1-2.0% of the total mass of the acrylic acid and the acrylamide monomer, and comprises an oxidant and a reducing agent, wherein the molar ratio of the oxidant to the reducing agent is (1-2): 1; the hectorite accounts for 5-20% of the total mass of the acrylic acid and the acrylamide monomers; the KH570 modified magnetic nanoparticles account for 5-30% of the total mass of acrylic acid and acrylamide monomers; the polyvinyl pyrrolidone accounts for 3-15% of the total mass of the acrylic acid and the acrylamide monomers;
D) the saturation magnetization of the magnetic hectorite composite polymer dye adsorbent is 3-14 emu/g, the remanence and the coercive force both tend to zero, the magnetic hectorite composite polymer dye adsorbent has paramagnetism and magnetic responsiveness, the gel strength of a water-absorbing gel is 5-20 Pa.s, the dye adsorption capacity reaches 50-560 mg/g for a dye aqueous solution with the initial concentration of 100-1000 mg/L, the adsorption balance is achieved within 60-120 min, and the dye adsorption capacity after 5 times of regeneration and cyclic utilization exceeds 90% of the first adsorption capacity.
2. The preparation method and the application of the magnetic hectorite composite polymer dye adsorbent for treating dye wastewater according to claim 1 are characterized in that: the cross-linking agent is selected from N, N' -methylene bisacrylamide, ethylene glycol diacrylate, monoethylene glycol diacrylate, diethylene glycol diacrylate, 1, 3-propylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, glycidyl methacrylate and polyethylene glycol diacrylate.
3. The preparation method and the application of the magnetic hectorite composite polymer dye adsorbent for treating dye wastewater according to claim 1 are characterized in that: the oxidant is selected from ammonium persulfate, potassium persulfate and sodium persulfate, and the reducer is selected from sodium bisulfite, sodium sulfite, sodium thiosulfate and ferrous sulfate.
4. The preparation method and the application of the magnetic hectorite composite polymer dye adsorbent for treating dye wastewater according to claim 1 are characterized in that: the dye is selected from methylene blue, cation blue FGL, cation orange R, cation bright yellow 7GL, cation peach red FG, methyl green, crystal violet, methyl orange, reactive black RB5, congo red, alizarin red, sunset yellow, alizarin green, acid chrome blue K and eosin Y.
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