CN115106519A - Superparamagnetic nano-iron material, composite material thereof, preparation method and application - Google Patents
Superparamagnetic nano-iron material, composite material thereof, preparation method and application Download PDFInfo
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- CN115106519A CN115106519A CN202210644231.0A CN202210644231A CN115106519A CN 115106519 A CN115106519 A CN 115106519A CN 202210644231 A CN202210644231 A CN 202210644231A CN 115106519 A CN115106519 A CN 115106519A
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- Prior art keywords
- iron
- nano
- superparamagnetic
- superparamagnetic nano
- reducing agent
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 150000002505 iron Chemical class 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 30
- 239000011591 potassium Substances 0.000 claims description 30
- 229910052700 potassium Inorganic materials 0.000 claims description 30
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 13
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 13
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 235000010755 mineral Nutrition 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005067 remediation Methods 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229960004887 ferric hydroxide Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 108010039918 Polylysine Proteins 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- 229960005191 ferric oxide Drugs 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-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
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229960003284 iron Drugs 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
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 claims description 2
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000656 polylysine Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 8
- -1 iron ions Chemical class 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
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- 238000005054 agglomeration Methods 0.000 abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 11
- 229960002089 ferrous chloride Drugs 0.000 description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229960000892 attapulgite Drugs 0.000 description 8
- 229910052625 palygorskite Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
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- 239000002689 soil Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910020068 MgAl Inorganic materials 0.000 description 5
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- 229920000742 Cotton Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
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- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
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- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
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- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a superparamagnetic nano-iron material, a composite material thereof, a preparation method and application. The preparation method of the superparamagnetic nano-iron material comprises the following steps: dissolving a certain amount of ferric salt and surface modification materials in deoxidized ethanol to obtain a mixed solution; weighing a reducing agent, dissolving the reducing agent in deoxidized ethanol, and adding ethylenediamine according to a certain proportion to prepare a mixed solution; according to the iron salt: and (2) dropwise adding a reducing agent solution into the mixture containing iron ions under the protection of nitrogen atmosphere and high-speed mechanical stirring with the molar ratio of the reducing agent being 1: 1-50, and continuously stirring and reacting for 10-30 min after dropwise adding is finished, so as to obtain the superparamagnetic nano iron material. The superparamagnetic nano-iron material and the composite material thereof have the advantages of good dispersibility, difficult agglomeration, good mobility in a saturated porous medium, high reaction activity, high electron utilization efficiency, capability of removing various pollutants and the like.
Description
Technical Field
The invention relates to the technical field of nano material preparation and environment restoration, in particular to a superparamagnetic nano iron material and a composite material thereof, and a preparation method and application thereof.
Background
The nano iron material has stronger reduction and catalysis effects and high reaction activity, and is widely used for removing organic pollutants and heavy metal ions in soil, underground water, rivers, lakes and industrial wastewater, such as reduction remediation of underground water polluted by chlorinated hydrocarbons, catalysis of Fenton to oxidize soil polluted by petroleum hydrocarbons and the like, autocatalysis of Fenton to oxidize salt-containing refractory organic wastewater and the like. The nano-iron material comprises nano zero-valent iron and oxides thereof, nano-iron material doped with dissimilar metals, nano-iron material compounded with biological carbon, graphene and natural minerals, and the like.
However, due to the inherent magnetic interaction between particles, the nano iron material is very easy to agglomerate into particles with micron or even millimeter sizes, so that the specific surface area of the nano iron material is reduced, the activity of the nano iron material is reduced, the transmission performance of the nano iron material in soil and underground water media is poor, and the treatment effect of the nano iron material is influenced. At present, the surface modification method is mainly used, for example, high molecular polymers such as carboxymethyl cellulose, PVP, PVA and the like are coated on the surface of the nano iron, so that the electric double layer repulsion between nano iron particles is enhanced, and the nano iron is prevented from agglomerating to enhance the migration performance and the reaction activity of the nano iron material. However, when the nano-iron material is dispersed in the water phase, relative motion always exists between the nano-iron materials due to a micro-convection phenomenon caused by brownian motion, and then induced current is generated under electromagnetic induction to destroy the double electric layers of the nano-iron material, thereby causing material agglomeration.
Disclosure of Invention
In order to solve the technical problems, the invention provides a superparamagnetic nano-iron material, a composite material thereof, a preparation method and application.
In a first aspect, the present invention provides a superparamagnetic nano-iron material, which is implemented by using the following technical scheme.
A superparamagnetic nano-iron material is a nano zero-valent iron material with superparamagnetic property, which is mainly prepared from iron salt and a reducing agent.
In a second aspect, the invention provides an application of a superparamagnetic nano-iron material, which is realized by adopting the following technical scheme.
The application of the superparamagnetic nano-iron material in environmental remediation is particularly used for remediating contaminated sites such as heavy metal and organochlorine compound contaminated soil, groundwater and the like, and degrading and removing heavy metal and organic pollutants in sewage and drinking water.
In a third aspect, the invention provides a preparation method of a superparamagnetic nano-iron material, which is realized by adopting the following technical scheme.
A preparation method of a superparamagnetic nano-iron material comprises the following steps:
s1, dissolving the ferric salt and the surface modification material in the deoxidized ethanol according to the molar ratio of 1: 0.5-20, and preparing a mixed solution of 5-400 g/L ferric salt and the surface modification material;
s2, weighing a reducing agent, dissolving the reducing agent in the deoxidized ethanol, and adding ethylenediamine into the reducing agent according to the molar ratio of 1: 0.01-1 of the reducing agent to the ethylenediamine to prepare a mixed solution;
s3, dropping the mixed solution obtained in the step S2 into the mixed solution obtained in the step S1 under the protection of nitrogen and high-speed mechanical stirring according to the molar ratio of the iron salt to the reducing agent of 1: 1-50, and continuing stirring and reacting for 10-30 min after dropping is finished to obtain the superparamagnetic nano iron material.
After the reaction is finished, putting the obtained superparamagnetic nano-iron material into a sealed bottle for storage; or drying in nitrogen atmosphere for long-term storage.
Further, the iron salt is selected from one or more of ferric chloride, ferrous sulfate, ferric carbonate, ferrous acetate, ferric citrate, ammonium ferrous sulfate, ferrous oxalate, ferric hydroxide, ferric oxide, iron rust and ferric sulfide, preferably the ferric chloride, the ferrous citrate, the ferrous oxalate and the iron oxide, and more preferably the ferric hydroxide, the ferric oxide and the iron rust.
Further, the molar ratio of the iron salt to the surface modification material is preferably 1: 5.
Further, the surface modification material is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, hexadecyl ammonium bromide, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polylysine, guar gum and rhamnolipid, and preferably carboxymethyl cellulose.
Further, the reducing agent is one or more selected from sodium hydrosulfite, thiourea dioxide, hydrazine hydrate, sodium borohydride and potassium borohydride, and preferably thiourea dioxide.
In a fourth aspect, the invention provides a superparamagnetic nano-iron composite material, which is realized by adopting the following technical scheme.
A superparamagnetic nano-iron composite material is a nano zero-valent iron composite material with superparamagnetic property, which is mainly prepared from ferric salt, a reducing agent and a doped composite material.
In a fifth aspect, the present application provides an application of a superparamagnetic nano-iron composite material, which is implemented by using the following technical scheme.
The application of the superparamagnetic nano-iron composite material in environmental remediation is particularly used for remediating contaminated sites such as heavy metal and organochlorine compound contaminated soil, groundwater and the like, and degrading and removing heavy metal and organic pollutants in sewage and drinking water.
In a sixth aspect, the invention provides a preparation method of a superparamagnetic nano-iron composite material, which is realized by adopting the following technical scheme.
A preparation method of a superparamagnetic nano-iron composite material comprises the following steps of adding iron salt and a surface modification material in a mixed solution obtained in the step S1, wherein the mass ratio of iron to a doped composite material is 1: the doped composite material is added in a proportion of 0.001-100.
Further, the mass ratio of the iron to the doped composite material is preferably 1: 5.
Further, the doped composite material is selected from one or more of metal salt, carbon material, sulfur material, metal oxide, metal hydroxide, natural fiber and natural mineral material.
Further, the sulfur material is selected from one or more of sublimed sulfur, sodium sulfide, potassium sulfide and iron sulfide, and preferably sodium sulfide.
Further, the metal salt is selected from one or more of calcium, magnesium, aluminum, manganese, cobalt, nickel, copper, zinc and palladium, and copper salt is preferred.
Further, the carbon material is selected from one or more of biochar, activated carbon, graphene, carbon nanotubes, carbon quantum dots, carbon fibers, graphite alkyne and silicon carbide, and preferably biochar.
Further, the metal oxide is selected from MgO and Al 2 O 3 、Fe 2 O 3 、CaO、CeO 2 、TiO 2 、MnO 2 、SiO 2 、ZnO、MgAl 2 O 4 、MnFe 2 O 4 、MgAl 2 O 4 、MgFe 2 O 4 、ZnFe 2 O 4 、ZnAl 2 O 4 Preferably Al 2 O 3 、Fe 2 O 3 、CaO、TiO 2 、MgAl 2 O 4 And MgFe 2 O 4 And the like have little influence on the environment.
Further, the metal hydroxide is selected from Mg (OH) 2 、Al(OH) 3 、AlOOH、Fe(OH) 3 CeOOH, MnOOH, MgAl two-dimensional layered double hydroxide, ZnAl two-dimensional layered double hydroxide, MgZnAl two-dimensional layered double hydroxide, MgFe two-dimensional layered double hydroxide, MgFeAl two-dimensional layered double hydrogenOne or more oxides, preferably Al (OH) 3 、AlOOH、Fe(OH) 3 And MgAl two-dimensional layered double hydroxide.
Further, the natural fiber material is selected from one or more of cellulose, chitosan, silk, bamboo fiber, flax fiber and cotton fiber, and preferably cellulose and cotton fiber.
Further, the natural mineral material is selected from one or more of vermiculite, montmorillonite, kaolin, attapulgite, basalt, rectorite, sepiolite, zeolite, diatomite, wollastonite, volcanic ash and tourmaline, and preferably montmorillonite and attapulgite.
The superparamagnetic nanoscale zero-valent iron and the composite material thereof prepared by the method comprise superparamagnetic vulcanized nanoscale zero-valent iron, superparamagnetic carbonized nanoscale zero-valent iron, bimetal-doped superparamagnetic nanoscale zero-valent iron, bimetal-doped carbonized nanoscale zero-valent iron, bimetal-doped superparamagnetic vulcanized nanoscale zero-valent iron, carbon-loaded superparamagnetic carbonized nanoscale zero-valent iron, carbon-loaded superparamagnetic vulcanized nanoscale zero-valent iron, metal oxide-loaded superparamagnetic carbonized nanoscale zero-valent iron, metal oxide-loaded superparamagnetic vulcanized nanoscale zero-valent iron, metal hydroxide-loaded superparamagnetic nano-carbonated nanoscale zero-valent iron, metal hydroxide-loaded superparamagnetic vulcanized nanoscale zero-valent iron, natural fiber material-loaded superparamagnetic nanoscale zero-valent iron, carbon-doped nanoscale zero-valent iron, metal oxide-doped carbon-valent iron, superparamagnetic nano zero-valent iron, and composite material thereof, Superparamagnetic carbonized nanometer zero-valent iron loaded by natural fiber materials, superparamagnetic vulcanized nanometer zero-valent iron loaded by natural fiber materials, superparamagnetic nanometer zero-valent iron loaded by natural minerals, superparamagnetic carbonized nanometer zero-valent iron loaded by natural minerals, vulcanized nanometer zero-valent iron loaded by natural minerals and the like all present superparamagnetic characteristics and take the zero-valent iron as a main component.
The present application has the following advantageous effects.
1. The superparamagnetic nano-iron material and the composite material particles thereof have no magnetic interaction, and when the superparamagnetic nano-iron material and the composite material particles are dispersed in a water phase, the superparamagnetic nano-iron material has good long-term stability, cannot generate agglomeration and sedimentation, and can fully exert the high-efficiency processing performance of the nano-iron material;
2. the superparamagnetic nano-iron material and the composite material thereof have the advantages of simple preparation method and low production cost, can effectively remove various organic pollutants and heavy metal ions in soil and water body environments, and have better effect and lower comprehensive cost when used for environmental remediation;
3. the preparation method of the superparamagnetic nano-iron material and the composite material thereof provided by the invention is easy to amplify and can directly realize industrial production.
Drawings
FIG. 1 is a TEM photograph of a superparamagnetic nano-iron material synthesized in example 1 of the present invention;
FIG. 2 is a hysteresis loop diagram of the superparamagnetic nano-iron material synthesized in example 1 of the present invention;
FIG. 3 is a photograph of an aqueous dispersion of superparamagnetic nano-iron material synthesized in example 1 of the present invention;
FIG. 4 is the dynamic curve of TCE degradation of superparamagnetic nano-iron material synthesized in example 1 of the present invention;
FIG. 5 shows the hydrogen evolution performance of the superparamagnetic nano-iron material synthesized in example 1 under the shaking table condition;
FIG. 6 is a hysteresis loop diagram of a superparamagnetic nano-iron material synthesized in example 2 of the present invention;
FIG. 7 is a hysteresis loop diagram of a superparamagnetic nano-iron material synthesized in example 3 of the present invention;
FIG. 8 is a hysteresis loop diagram of the superparamagnetic nano-iron material synthesized in example 4 of the present invention.
Detailed Description
The patent application is further described below with reference to the drawings and examples.
Example 1
In the embodiment, potassium borohydride is used for reducing ferrous chloride to prepare a superparamagnetic nano-iron material, and the preparation steps are as follows:
1) according to the weight ratio of Fe: carboxymethyl cellulose =1:2 molar ratio, ferrous chloride and sodium carboxymethyl cellulose are weighed and added into deoxyethanol, stirred and dissolved, and Fe with the mass concentration of 20 g/L is obtained by constant volume 2+ Solutions of；
2) Weighing a certain amount of potassium borohydride, adding the potassium borohydride into the deoxyethanol, stirring and dissolving, and fixing the volume to obtain a potassium borohydride solution with the mass concentration of 40 g/L; according to the proportion of potassium borohydride: adding ethylenediamine into the potassium borohydride solution according to the molar ratio of 10: 1;
3) under vigorous mechanical stirring and nitrogen protection, the ratio of the iron to the iron in terms of Fe: dropwise adding the solution obtained in the step 2 into the solution obtained in the step 1 according to the molar ratio of potassium borohydride =1:3, and continuously stirring and reacting for 20 min after dropwise adding;
4) and (3) washing the nano iron material prepared in the step (3) with absolute ethyl alcohol, removing soluble salt ions and impurities, and drying under nitrogen atmosphere to obtain the superparamagnetic nano iron material.
Referring to fig. 1 and 2, it can be seen from fig. 1 that the synthesized superparamagnetic nano-iron material is a cluster composed of nano-iron particles. The hysteresis loop of figure 2 shows that it has no obvious hysteresis loop, and the room temperature remanence and coercive force are respectively 0.86 emu g -1 And 2.63 Oe, exhibit significant superparamagnetic properties.
FIG. 3 shows that the aqueous dispersion of the synthetic material of this example shows strong stability, no obvious agglomeration and sedimentation after standing for 6.5 days, and good long-term stability. As can be seen from the enlarged partial view in the figure (red box), little hydrogen gas is generated after standing for 6.5d, which indicates that the tendency of the superparamagnetic nano-iron cluster to corrode and evolve hydrogen is weak.
FIG. 4 shows that the material synthesized in this example is used for reducing and degrading trichloroethylene as a contaminant, and a shaking table experiment is adopted to test the degradation performance of the superparamagnetic nano-iron cluster on trichloroethylene, wherein the concentration of TCE is 10 mg/L, and the dosage of the superparamagnetic nano-iron cluster is 2 g/L. The figure shows that the superparamagnetic nano iron shows faster degradation kinetics to TCE, and TCE can be completely degraded and dechlorinated in 24 hours. The corrosion hydrogen evolution performance of the catalyst is much weaker than that of the common nZVI (figure 5), the hydrogen production data is fitted through a first-order reaction kinetic equation, and the rate constant of the corrosion hydrogen evolution reaction is calculated to be 0.019d -1 The lifetime was estimated to be 53 days, much higher than normal nZVI.
Example 2
In this embodiment, a mixed solution of ferrous chloride and nickel chloride is reduced by potassium borohydride to prepare a superparamagnetic nano iron-nickel composite material, which includes the following specific steps:
1) according to the weight ratio of Fe: ni: carboxymethyl cellulose =1:0.05:5, ferrous chloride, nickel chloride and carboxymethyl cellulose are weighed and added into deoxidized ethanol, stirred and dissolved, and Fe with the mass concentration of 20 g/L is obtained by constant volume 2+ Mixing the solution;
2) weighing a certain amount of potassium borohydride, adding the potassium borohydride into the deoxyethanol, stirring and dissolving, and fixing the volume to obtain a potassium borohydride solution with the mass concentration of 40 g/L; according to the proportion of potassium borohydride: adding ethylenediamine into the potassium borohydride solution according to the molar ratio of 10: 1;
3) under vigorous mechanical stirring and nitrogen protection, the ratio of Fe: dropwise adding the solution obtained in the step 2 into the solution obtained in the step 1 according to the molar ratio of potassium borohydride =1:3, and continuously stirring and reacting for 20 min after dropwise adding;
4) and (3) washing the nano iron material prepared in the step (3) with absolute ethyl alcohol, removing soluble salt ions and impurities, and drying under nitrogen atmosphere to obtain the superparamagnetic nano iron-nickel composite material.
Fig. 6 is a hysteresis loop of the superparamagnetic nano-iron-nickel composite material synthesized in this embodiment, and it can be seen that the material exhibits a distinct superparamagnetic property.
Example 3
In the embodiment, potassium borohydride is used for reducing ferrous chloride to prepare the attapulgite loaded superparamagnetic nano-iron composite material, and the preparation method specifically comprises the following steps:
1) according to the weight ratio of Fe: weighing ferrous chloride and carboxymethyl cellulose according to the molar ratio of carboxymethyl cellulose =1:2, adding the weighed ferrous chloride and carboxymethyl cellulose into deoxidized ethanol, stirring and dissolving the materials, and fixing the volume to obtain Fe with the mass concentration of 20 g/L 2+ The solution was mixed. According to the weight ratio of Fe: weighing attapulgite according to the mass ratio of the attapulgite =1:5, adding the attapulgite into the mixed solution, and uniformly stirring;
2) weighing a certain amount of potassium borohydride, adding the potassium borohydride into the deoxyethanol, stirring and dissolving, and fixing the volume to obtain a potassium borohydride solution with the mass concentration of 40 g/L; according to the proportion of potassium borohydride: adding ethylenediamine into the potassium borohydride solution according to the molar ratio of 10: 1;
3) under vigorous mechanical stirring and nitrogen protection, the ratio of Fe: dropwise adding the solution obtained in the step 2 into the solution obtained in the step 1 according to the molar ratio of potassium borohydride =1:2, and continuously stirring and reacting for 20 min after dropwise adding;
4) and (3) washing the nano-iron material prepared in the step (3) with absolute ethyl alcohol, removing soluble salt ions and impurities, and drying under nitrogen atmosphere to obtain the attapulgite loaded superparamagnetic nano-iron composite material.
Fig. 7 is a hysteresis loop of the superparamagnetic nano-iron composite material loaded with attapulgite synthesized in this example, which exhibits a significant superparamagnetic property.
Example 4
In the embodiment, potassium borohydride is used as a reducing agent to prepare the superparamagnetic nano-iron composite loaded by the magnesium-aluminum bimetal hydroxide, and the preparation method specifically comprises the following steps:
1) according to the weight ratio of Fe: weighing ferrous chloride and carboxymethyl cellulose according to the molar ratio of carboxymethyl cellulose =1:1, adding the weighed ferrous chloride and carboxymethyl cellulose into deoxidized ethanol, stirring and dissolving the materials, and fixing the volume to obtain Fe with the mass concentration of 20 g/L 2+ The solution was mixed. According to the weight ratio of Fe: weighing magnesium-aluminum bimetal hydroxide according to the mass ratio of magnesium-aluminum bimetal hydroxide =1:3, adding the magnesium-aluminum bimetal hydroxide into the mixed solution, and uniformly stirring;
2) weighing a certain amount of potassium borohydride, adding the potassium borohydride into the deoxyethanol, stirring and dissolving, and fixing the volume to obtain a potassium borohydride solution with the mass concentration of 40 g/L; according to the proportion of potassium borohydride: adding ethylenediamine into the potassium borohydride solution according to the molar ratio of 20: 1;
3) under vigorous mechanical stirring and nitrogen protection, the ratio of Fe: dropwise adding the solution obtained in the step 2 into the solution obtained in the step 1 according to the mass ratio of potassium borohydride =1:2.5, and continuously stirring and reacting for 20 min after dropwise adding;
4) and (3) washing the nano-iron material prepared in the step (3) with absolute ethyl alcohol, removing soluble salt ions and impurities, and drying under nitrogen atmosphere to obtain the magnesium-aluminum bimetal hydroxide loaded superparamagnetic nano-iron composite material.
Fig. 8 is a hysteresis loop of the superparamagnetic nano-iron composite loaded with magnesium aluminum double hydroxide synthesized in this example, which exhibits a significant superparamagnetic property.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (10)
1. A superparamagnetic nano-iron material is characterized in that: the superparamagnetic nano-iron material is a nano zero-valent iron material with superparamagnetic property, which is mainly prepared from iron salt and a reducing agent.
2. Use of the superparamagnetic nano-iron material of claim 1 in environmental remediation.
3. A method for preparing superparamagnetic nano-iron as recited in claim 1, characterized by: the method comprises the following steps:
s1, dissolving the ferric salt and the surface modification material in the deoxidized ethanol according to the molar ratio of 1: 0.5-20, and preparing a mixed solution of 5-400 g/L ferric salt and the surface modification material;
s2, weighing a reducing agent, dissolving the reducing agent in the deoxidized ethanol, and adding ethylenediamine into the reducing agent according to the molar ratio of 1: 0.01-1 of the reducing agent to the ethylenediamine to prepare a mixed solution;
s3, dropping the mixed solution obtained in the step S2 into the mixed solution obtained in the step S1 under the protection of nitrogen and high-speed mechanical stirring according to the molar ratio of the iron salt to the reducing agent of 1: 1-50, and continuing stirring and reacting for 10-30 min after dropping is finished to obtain the superparamagnetic nano iron material.
4. The method for preparing superparamagnetic nano-iron material according to claim 3, wherein: the ferric salt is selected from one or more of ferric chloride, ferrous sulfate, ferric carbonate, ferrous acetate, ferric citrate, ammonium ferrous sulfate, ferrous oxalate, ferric hydroxide, ferric oxide, iron rust and ferric sulfide.
5. The method for preparing superparamagnetic nano-iron material according to claim 3, wherein: the surface modification material is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, hexadecyl ammonium bromide, carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polylysine, guar gum and rhamnolipid.
6. The method for preparing superparamagnetic nano-iron material according to claim 3, wherein: the reducing agent is selected from one or more of sodium hydrosulfite, thiourea dioxide, hydrazine hydrate, sodium borohydride and potassium borohydride.
7. A superparamagnetic nano-iron composite material is characterized in that: the superparamagnetic nano-iron composite material is a nano zero-valent iron composite material with superparamagnetic property, which is mainly prepared from iron salt, a reducing agent and a doped composite material.
8. Use of the superparamagnetic nano-iron composite of claim 7 in environmental remediation.
9. A method for preparing the superparamagnetic nano-iron composite material as recited in claim 7, characterized by: adding the iron salt and the surface modification material mixed solution obtained in the step S1 of any one of claims 3 to 6, wherein the mass ratio of iron to the doped composite material is 1: the doped composite material is added in a proportion of 0.001-100.
10. The method for preparing superparamagnetic nano-iron composite material according to claim 9, wherein: the doped composite material is selected from one or more of metal salt, carbon material, sulfur material, metal oxide, metal hydroxide, natural fiber and natural mineral material.
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