CN111266572A - Iron-copper bimetal load ferrous sulfide composite material, preparation method and application thereof - Google Patents
Iron-copper bimetal load ferrous sulfide composite material, preparation method and application thereof Download PDFInfo
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- CN111266572A CN111266572A CN202010200466.1A CN202010200466A CN111266572A CN 111266572 A CN111266572 A CN 111266572A CN 202010200466 A CN202010200466 A CN 202010200466A CN 111266572 A CN111266572 A CN 111266572A
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- iron
- copper
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- iron powder
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- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 162
- 239000000243 solution Substances 0.000 claims abstract description 77
- 239000011651 chromium Substances 0.000 claims abstract description 52
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000001879 copper Chemical class 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims abstract description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 8
- 238000005067 remediation Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000003828 vacuum filtration Methods 0.000 claims description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 11
- 238000010926 purge Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910001018 Cast iron Inorganic materials 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000007974 sodium acetate buffer Substances 0.000 claims description 7
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000003673 groundwater Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 26
- 238000006073 displacement reaction Methods 0.000 description 14
- 238000011056 performance test Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000000227 grinding Methods 0.000 description 11
- 238000010998 test method Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 150000002505 iron Chemical class 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- -1 sulfide ions Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B22F1/0003—
-
- 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
-
- 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
-
- 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
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention relates to an iron-copper bimetal load ferrous sulfide composite material, a preparation method and application thereof. The composite material comprises iron-copper bimetal and ferrous sulfide loaded on the surface of the iron-copper bimetal, wherein copper in the iron-copper bimetal is loaded on the surface of iron. The composite material has high activity and reaction selectivity, and can be used in the fields of chromium-containing sewage treatment, chromium-polluted underground water remediation and the like. The preparation method comprises the following steps: and mixing the copper salt solution and the iron powder for the first time, and then mixing the mixture and the alkali metal sulfide solution for the second time to obtain the iron-copper bimetal load ferrous sulfide composite material. The preparation method recovers the F generated in the replacement process of copper ions and iron powdere2+Has the advantages of simple steps, economy and effectiveness.
Description
Technical Field
The invention relates to the technical field of environmental remediation, in particular to an iron-copper bimetal load ferrous sulfide composite material, and a preparation method and application thereof.
Background
The problem of water environment pollution is one of the main environmental problems, zero-valent iron is used as an environment-friendly material which does not generate secondary pollutants and has a removal effect on various pollutants, more and more researchers apply the zero-valent iron to water treatment, but the main problem existing at present is that the surface of the zero-valent iron is easy to passivate, so that the reaction activity is reduced. In order to increase the activity of zero-valent iron, researchers have proposed many countermeasures, such as acid-washing zero-valent iron, nano-zero-valent iron, bimetallic, etc.
CN108249524A discloses a zero-valent iron-copper micro-electrolysis filler and a preparation method thereof, wherein the preparation method mainly comprises the following steps: (1) plating a layer of compact copper on the surface of zero-valent iron to prepare an iron-copper bimetal; (2) cleaning and drying; (3) mixing to obtain a filler; the material in the patent improves the activity of zero-valent iron by utilizing iron-copper micro-electrolysis and increases the utilization efficiency of the zero-valent iron, but the material has the defects that a passivation layer is formed too fast and the reaction selectivity of the zero-valent iron is reduced.
CN105195758A discloses a preparation method and application of nano zero-valent iron-copper bimetallic particles. The preparation method comprises the following steps: adding iron salt and copper salt into a three-neck flask according to the molar ratio of 3-10: 1; adding 50-100 mL of ethanol solution into a three-neck flask, and stirring in a water bath at 20-60 ℃ for 10-30 min; adding a borohydride solution into a three-neck flask, stirring for 10-40 min, and performing suction filtration to obtain a precipitate; and washing the precipitate with absolute ethyl alcohol and acetone respectively, then carrying out suction filtration, and drying in a vacuum drying oven at 25-80 ℃ for 1-24 h to obtain the nano zero-valent iron-copper bimetallic particles. The nanometer material obtained by the invention has high activity, and can easily react with water directly during application, so that the material is inactivated.
However, with the progress of the research, the researchers found that: in an aquatic environment system, zero-valent iron is not a direct ironReducing agent of (1), Fe produced by oxidation of zero-valent iron2+Plays a key role in reduction. In recent years, ferrous sulfide has reducibility and is a common precursor of pyrite in nature, and environment-friendly ferrous sulfide gradually becomes a research hotspot.
CN106536097A discloses a preparation method of an iron-ferrous sulfide complex, which comprises the following steps: mixing elemental sulfur powder and ferrous sulfide powder in a mass ratio of 1: 5-60 or pyrite powder and micron-sized iron powder in a mass ratio of 1: 5-60 to obtain a mixed raw material, placing the mixed raw material in a ball milling tank of a ball mill, filling a grinding medium in the ball milling tank, starting the ball mill in a vacuum environment or an inert gas atmosphere in the ball milling tank, grinding at a grinding speed of 400-4000 rpm for 2-30 hours, and separating the grinding medium from a product after grinding to obtain an iron-ferrous sulfide complex with a particle size of less than 10 microns. Although the iron-ferrous sulfide complex prepared in the invention improves the electron selectivity of zero-valent iron, the utilization rate of the zero-valent iron is lower.
Based on the research of the prior art, how to develop an iron-copper bimetal composite material, improve the reactivity of zero-valent iron and the selectivity of the material, shorten the preparation process flow and improve the utilization rate of raw materials becomes a technical problem to be solved urgently at present.
Disclosure of Invention
In view of the problems in the prior art, the invention provides an iron-copper bimetal load ferrous sulfide composite material, a preparation method and application thereof. In the composite material, the reaction activity of zero-valent iron is improved by forming a copper-iron micro primary battery, and the reaction selectivity of the material is improved by loading ferrous sulfide on the surface of iron-copper bimetal; the preparation method is simple in process, economical and effective, and has good application prospects in the aspects of chromium-containing sewage treatment, groundwater remediation and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an iron-copper bimetal loaded ferrous sulfide composite material, which comprises an iron-copper bimetal and ferrous sulfide loaded on the surface of the iron-copper bimetal, wherein copper in the iron-copper bimetal is loaded on the surface of iron and partially covers the surface of the iron.
In the invention, the "copper-iron bimetal" refers to bimetal formed by a copper simple substance and an iron simple substance.
According to the composite material provided by the invention, copper is loaded on the iron surface and partially covers the iron surface, so that iron-copper bimetal forms a tiny primary battery, the reaction activity of zero-valent iron is improved, and the utilization rate of the zero-valent iron is further improved; the ferrous sulfide loaded on the surface of the iron-copper bimetal not only reduces the problem of overhigh passivation speed of the iron-copper bimetal, but also reduces the water corrosion of zero-valent iron and improves the reaction selectivity of the material; in addition, compared with iron hydroxide, the ferrous sulfide loaded on the iron surface is a good electronic conductor, and the ferrous sulfide loaded on the copper surface can be used as an effective reducing agent to react with hexavalent chromium, so that the reaction selectivity of the material is further improved. The composite material can effectively remove chromium, and the chromium removal efficiency can reach more than 45% under the condition that no electrolyte is added and the pH value is neutral.
Preferably, the molar ratio of copper to iron in the composite material is (0.01 to 0.12):1, and may be, for example, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1, or 0.12:1, but is not limited to the recited values, and other values within the range are also applicable, and (0.04 to 0.07):1 is preferred. If the molar ratio is less than 0.01:1, a copper-iron bimetal with a large specific surface cannot be formed, so that the load of FeS is not facilitated; the molar ratio is more than 0.12:1, and the content of iron is too low, resulting in a decrease in reactivity.
Preferably, the molar ratio of the sulfur element to the iron element in the composite material is (0.01 to 0.12):1, and may be, for example, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1, or 0.12:1, but not limited to the enumerated values, and other non-enumerated values within the numerical range are also applicable, and are preferably (0.05 to 0.08): 1. If the molar ratio is less than 0.01:1, the amount of ferrous sulfide is too small, the specific surface area cannot be increased, and the electron efficiency is reduced; the molar ratio is more than 0.12:1, the amount of ferrous sulfide is too much, and the ferrous sulfide is accumulated on the surface of the bimetal to prevent the bimetal from contacting with pollutants in a solution, so that the reactivity of the material is seriously influenced.
Preferably, the specific surface area of the composite material is 10-30 m2Per g, may be, for example, 10m2/g、13m2/g、14m2/g、16m2/g、19m2/g、20m2/g、25m2/g、30m2And/g, but not limited to, the recited values, and other values not recited within the range of values are also applicable, preferably 15 to 25m2(ii)/g; the specific surface area of the composite material is improved by 14-20 times compared with that of the original iron powder and 2-3 times compared with that of the iron-copper bimetal.
In a second aspect, the present invention provides a method of making a composite material as defined in the first aspect, the method comprising the steps of:
and mixing the copper salt solution and the iron powder for the first time, and then mixing the mixture and the alkali metal sulfide solution for the second time to obtain the iron-copper bimetal load ferrous sulfide composite material.
According to the preparation method provided by the invention, a copper salt solution is mixed with iron powder, copper ions and an iron simple substance undergo a displacement reaction, and generated copper grows on the surface of the iron powder in situ to form a tiny primary battery, so that the corrosion of the iron simple substance is accelerated, and the reaction activity of zero-valent iron is improved; adding alkali metal sulfide solution into the solution after reaction, and reacting sulfide ions with Fe generated by replacement reaction2+The coprecipitation is carried out to generate ferrous sulfide which is loaded on the surface of the copper-iron bimetal, so that the reaction selectivity of the material is improved. The method makes full use of Fe generated by the replacement reaction2+The method not only improves the utilization rate of the raw materials, but also improves the removal efficiency of the material to the hexavalent chromium, and has the characteristics of simple preparation process, economy and effectiveness, and higher application value.
In the invention, before primary mixing, the copper salt can be prepared into a solution and then mixed with the acidic solution, or the copper salt can be directly mixed with the acidic solution.
Preferably, before the first mixing, the copper salt solution is mixed with an acidic solution, and the acidic solution can remove an oxide layer on the surface of the iron powder, so that more active sites are provided for the subsequent displacement reaction, and the displacement reaction is more sufficient.
Preferably, the acidic solution comprises an acetic acid buffer solution and/or a hydrochloric acid solution, preferably an acetic acid buffer solution.
Preferably, the pH of the acidic solution is 4 to 6.9, for example, 4, 4.5, 5, 5.5, 6, 6.5, or 6.9, but not limited to the values listed, and other values not listed within this range are also applicable, preferably 5.5 to 6.5. If the pH is less than 4, a large amount of iron powder will be dissolved, resulting in loss of iron; if the pH is more than 6.9, the surface oxide cannot be removed, and the reactivity of the finally obtained material is weakened.
Preferably, the copper salt solution is mixed with the acidic solution to remove dissolved oxygen therefrom.
In the present invention, the method for removing dissolved oxygen is not particularly limited, and any method commonly used by those skilled in the art can be applied to the present invention.
Preferably, the method of removing dissolved oxygen comprises purging with nitrogen and/or an inert gas.
Preferably, the inert gas comprises argon and/or helium.
Preferably, the copper salt comprises any one of copper chloride, copper sulfate or copper nitrate or a combination of at least two of them, wherein typical but non-limiting combinations are: copper chloride and sulfate, copper sulfate and nitrate.
Preferably, the concentration of copper ions in the copper salt solution is 0.89 to 10.7mmol/L, for example, 0.89mmol/L, 0.9mmol/L, 1.8mmol/L, 2.1mmol/L, 3.4mmol/L, 7.5mmol/L, 8.6mmol/L, 9.6mmol/L, or 10.7mmol/L, but not limited to the values listed, and other values not listed in the range of values are also applicable, preferably 3.5 to 6.2 mmol/L.
Preferably, the molar ratio of the copper element in the copper salt solution to the iron element in the iron powder is (0.01 to 0.12):1, and may be, for example, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1, or 0.12:1, but is not limited to the enumerated values, and other enumerated values within the numerical range are equally applicable, and preferably (0.04 to 0.07): 1. If the molar ratio is less than 0.01:1, the copper-iron primary battery has weak effect, the particle surface is not rough enough, and the load of FeS in the next step is not facilitated; the molar ratio is more than 0.12:1, so that the content of zero-valent iron is relatively reduced, the effect of the primary battery is weaker and weaker, even the primary battery cannot be formed, and the reduction effect is reduced.
Preferably, the iron powder comprises any one of reduced iron powder, cast iron powder or recycled iron powder or a combination of at least two thereof, among which typical but non-limiting combinations are: reduced iron powder and cast iron powder, reduced iron powder and regenerated iron powder, cast iron powder and regenerated iron powder.
Preferably, the particle size of the iron powder is 100 to 600 mesh, which is a micron-sized iron powder, and for example, the particle size may be 100 mesh, 200 mesh, 300 mesh, 400 mesh, 500 mesh, 600 mesh, etc., but the particle size is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, and 325 to 600 mesh is preferable. If the particle size of the iron powder is smaller than 600 meshes, although the prepared material has high reactivity, the cost is greatly increased, and if the particle size is larger than 100 meshes, the prepared material has too low reactivity.
Preferably, the purity of the iron powder is 80 to 99%, for example, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98%, 99%, etc., but is not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 90 to 98%. If the purity is too low, the uniformity of the displacement reaction is affected, the displacement reaction is more uniform as the purity is higher, the displacement reaction is incomplete due to too short reaction time, the iron-copper bimetal cannot be formed, the reaction time is too long, and the activity of the material is reduced due to the hydrogen evolution reaction of the material and water.
Preferably, the time for the first mixing is 5 to 60min, for example, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, etc., but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, preferably 20 to 40 min.
Preferably, the temperature of the first mixing is 25 to 60 ℃, for example, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 55 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 25 to 30 ℃.
Preferably, the heating mode of the primary mixing comprises any one or the combination of at least two of direct heating by an electric hot plate, microwave heating, water bath heating or oil bath heating, and preferably the water bath heating.
Preferably, the means for mixing at one time comprises stirring.
Preferably, the rotation speed of the stirring is 30 to 400rpm, for example, 30rpm, 40rpm, 80rpm, 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 380rpm or 400rpm, etc., but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable, preferably 200 to 300 rpm.
Preferably, the alkali metal sulphide salt comprises any one or a combination of at least two of sodium sulphide, potassium sulphide or lithium sulphide, preferably sodium sulphide.
In the invention, the alkali metal sulfide salt can directly participate in the reaction, and can also participate in the reaction after being prepared into a solution.
Preferably, the concentration of the alkali metal sulfide solution is 0.5 to 2mol/L, and may be, for example, 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, or 2mol/L, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable, and preferably 1 to 2 mol/L.
Preferably, the molar ratio of the amount of the sulfur element added to the iron element in the iron powder in the alkali metal sulfide solution is (0.01 to 0.12):1, and may be, for example, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1 or 0.12:1, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable, and (0.05 to 0.08):1 is preferable.
In the present invention, S in the alkali metal sulfide salt2-Can be used forEffective with Fe2+Coprecipitation to produce ferrous sulfide, thereby improving the selectivity of the material to the reaction of pollutants, but S2-Too much addition results in a decrease in the specific surface area and thus a decrease in the number of active sites on the surface of the material.
Preferably, the time for the secondary mixing is 1 to 12 hours, for example, 1 hour, 1.5 hours, 3 hours, 5 hours, 6 hours, 8 hours, 10 hours, or 12 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 5 to 8 hours. If the time is less than 1h, ferrous sulfide can not be loaded on the surface of the iron-copper bimetal, and if the time is more than 12h, the activity of the material is reduced.
Preferably, the method further comprises: after the reaction of step (2), isolation is carried out.
Preferably, the separation means comprises any one or a combination of at least two of pressure filtration, vacuum filtration or centrifugation, preferably vacuum filtration.
Preferably, the method further comprises: the solid phase obtained by separation is dried.
Preferably, the drying means comprises any one or a combination of at least two of vacuum drying, freeze drying or vacuum freeze drying, preferably vacuum freeze drying.
As a further preferred embodiment of the present invention, the method comprises the steps of:
(1) adding copper salt into acetic acid-sodium acetate buffer solution with the pH value of 5.5-6.5, and mixing to ensure that the concentration of copper ions is 3.5-6.2 mmol/L;
the copper salt comprises any one or the combination of at least two of copper chloride, copper sulfate or copper nitrate solution;
(2) removing dissolved oxygen from the solution using an inert gas purge and sealing the solution system;
(3) adding 325-600 meshes of iron powder with the purity of 90-98% into the solution system, controlling the molar ratio of copper elements in the copper salt solution to iron elements in the iron powder to be (0.04-0.07): 1, stirring at the temperature of 25-30 ℃ and the rotating speed of 200-300 rpm, heating in a water bath, and reacting for 20-40 min;
the iron powder comprises any one or the combination of at least two of reduced iron powder, cast iron powder or regenerated iron powder;
(4) adding Na with the concentration of 1-2 mol/L into the solution after the reaction in the step (3)2And (2) controlling the molar ratio of the sulfur element to the iron element in the iron powder to be (0.05-0.08): 1, reacting for 5-8 h, carrying out vacuum filtration on the mixed solution system by using a 0.22 mu m water system filter membrane to obtain filter residue, and finally carrying out vacuum freeze drying on the filter residue to obtain the iron-copper bimetal load ferrous sulfide composite material.
In a third aspect, the invention provides a use of the iron-copper bimetal loaded ferrous sulfide composite material as described in the first aspect, and the composite material is applied to the fields of chromium-containing wastewater treatment and chromium-polluted groundwater remediation.
In the invention, the chromium-containing wastewater refers to wastewater with high chromium content discharged in industrial production, and the treatment refers to sewage treatment technologies such as pool purification and the like; the chromium-polluted underground water refers to an underground water source polluted by hexavalent chromium, and the repairing refers to an in-situ repairing technology for repairing hexavalent chromium in an underground water aquifer.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the iron-copper bimetal loaded ferrous sulfide composite material provided by the invention, the iron simple substance is loaded on the surface of the copper simple substance and partially covers the surface of the copper simple substance to form a tiny primary battery, so that the reaction activity of zero-valent iron is improved, the ferrous sulfide loaded on the surface of the iron-copper bimetal not only improves the utilization rate of the zero-valent iron and slows down the problem of overhigh passivation speed of the iron-copper bimetal, but also can slow down the water corrosion of the zero-valent iron, thereby improving the reaction selectivity of the material; in a chromium removal performance test, the chromium removal efficiency is good, and can reach more than 45% in 3h under the condition that no electrolyte is added and the pH is neutral;
(2) the preparation method provided by the invention combines the preparation process of the iron-copper bimetal with the preparation process of the ferrous sulfide, and can generate the elementary copper substance on the surface of the zero-valent iron in situ through the replacement reaction of the copper ions and the elementary iron substanceForm a tiny primary battery, accelerate the corrosion of iron, improve the reaction activity of materials, and recover the Fe generated in the replacement process of copper ions and iron simple substances by adding sulfide ions2+The method has the advantages of simple preparation steps, economy and effectiveness.
Drawings
FIG. 1 is a scanning electron micrograph of the composite material prepared in example 1.
Fig. 2(a) -2 (b) are a scanning electron micrograph and an electron energy spectrum, respectively, of the composite material prepared in example 2.
FIGS. 3(a) -3 (b) are graphs comparing the curves of the tests for the dechroming performance of the iron sulfonate of the composites of examples 1-5 and comparative example 2 and the effect of the addition of copper on the dechroming efficiency of the iron-copper bimetallic supported ferrous sulfide, respectively.
FIG. 4 is a scanning electron microscope image of the bimetal Fe-Cu prepared in comparative example 1 of the present invention.
FIG. 5 is a scanning electron micrograph of sulfonated iron prepared according to comparative example 2 of the present invention.
Fig. 6 is a scanning electron micrograph of a comparative example 3 of the original iron powder of the present invention.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) preparing 200mL acetic acid-sodium acetate buffer solution with pH of 6, adding 0.4mmol copper chloride, and mixing uniformly;
(2) removing dissolved oxygen from the solution in step (1) by nitrogen purging, and sealing by using a film;
(3) adding 1g of micron-sized iron powder with the size of 400 meshes and the purity of 98% into the solution in the step (2), and fully performing a displacement reaction for 30min in a water bath shaking table with the temperature of 25 ℃ and the rotating speed of 200 rpm;
(4) after the reaction in step (3)2mL of 0.5mol/L Na was added to the solution2And (3) fully reacting the S solution for 8 hours, performing vacuum filtration by using a 0.22 mu m water system filter membrane to obtain filter residues, and finally performing vacuum freeze drying to obtain the iron-copper bimetal load ferrous sulfide composite material.
The morphology of the iron-copper bimetallic load ferrous sulfide composite material prepared in this example is shown in fig. 1. The specific surface area of the iron-copper bimetal load ferrous sulfide composite material is 13m2/g。
The composite material prepared in this example was subjected to a chromium removal performance test, the test method being: the experimental conditions are water bath at 25 ℃, mechanical stirring at 300rpm, initial concentration of Cr (VI) solution of 5mg/L, volume of 1L, material addition of 0.2g/L (without any electrolyte), chromium removal efficiency of 59% at 3h, and concentration change curve shown in figure 3 (a).
Example 2
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) preparing 200mL acetic acid-sodium acetate buffer solution with pH of 6, adding 0.8mmol copper chloride, and mixing uniformly;
(2) removing dissolved oxygen from the solution in step (1) by nitrogen purging, and sealing by using a film;
(3) adding 1g of micron-sized iron powder with the size of 400 meshes and the purity of 98% into the solution in the step (2), and fully performing a displacement reaction for 30min in a water bath shaking table with the temperature of 25 ℃ and the rotating speed of 200 rpm;
(4) 2mL of 0.5mol/L Na was added to the reacted solution in the step (3)2And (3) fully reacting the S solution for 6 hours, performing vacuum filtration by using a 0.22 mu m water system filter membrane to obtain filter residues, and finally performing vacuum freeze drying to obtain the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetal load ferrous sulfide composite material prepared by the embodiment is 19m2/g。
Fig. 2(a) -2 (b) are a scanning electron micrograph and an electron energy spectrogram of the iron-copper bimetallic supported ferrous sulfide composite material prepared in this example, and the electron energy spectrogram of fig. 2(b) is a characterization result of a box labeled area in fig. 2(a), which indicates that the iron-copper bimetallic supported ferrous sulfide composite material prepared in this example is obtained.
The composite material prepared in this example was tested for chromium removal performance in the same manner as in example 1, and it was found that the chromium removal efficiency was 67% at 3 hours, and the concentration change curve is shown in fig. 3 (a).
Example 3
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) preparing 200mL acetic acid-sodium acetate buffer solution with pH of 6, adding 1.2mmol copper chloride, and mixing uniformly;
(2) removing dissolved oxygen from the solution in step (1) by nitrogen purging, and sealing by using a film;
(3) adding 1g of micron-sized iron powder with the size of 400 meshes and the purity of 98% into the solution in the step (2), and fully performing a displacement reaction for 30min in a water bath shaking table with the temperature of 25 ℃ and the rotating speed of 200 rpm;
(4) 2mL of 0.5mol/L Na was added to the reacted solution in the step (3)2And (3) fully reacting the S solution for 6 hours, performing vacuum filtration by using a 0.22 mu m water system filter membrane to obtain filter residues, and finally performing vacuum freeze drying to obtain the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetal load ferrous sulfide composite material prepared by the embodiment is 16m2/g。
The composite material prepared in this example was tested for chromium removal performance in the same manner as in example 1, and the chromium removal efficiency was 60% at 3h, as shown in fig. 3 (a).
Example 4
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) preparing 200mL acetic acid-sodium acetate buffer solution with pH of 6, adding 1.6mmol copper chloride, and mixing uniformly;
(2) removing dissolved oxygen from the solution in step (1) by nitrogen purging, and sealing by using a film;
(3) and (3) adding 1g of micron-sized iron powder with the size of 400 meshes and the purity of 98% into the solution in the step (2), and fully performing a displacement reaction for 30min in a water bath shaking table with the temperature of 25 ℃ and the rotating speed of 200 rpm.
(4) 2mL of 0.5mol/L Na was added to the reacted solution in the step (3)2And (3) fully reacting the S solution for 6 hours, performing vacuum filtration by using a 0.22 mu m water system filter membrane to obtain filter residues, and finally performing vacuum freeze drying to obtain the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetallic load ferrous sulfide composite material prepared by the embodiment is 14m2/g。
The composite material prepared in this example was tested for chromium removal performance in the same manner as in example 1, and found to have a chromium removal efficiency of 57% at 3h, with the concentration change curve shown in fig. 3 (a).
Example 5
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) preparing 200mL acetic acid-sodium acetate buffer solution with pH of 6, adding 2.0mmol copper chloride, and mixing uniformly;
(2) removing dissolved oxygen from the solution in step (1) by nitrogen purging, and sealing by using a film;
(3) and (3) adding 1g of micron-sized iron powder with the size of 400 meshes and the purity of 98% into the solution in the step (2), and fully performing a displacement reaction for 30min in a water bath shaking table with the temperature of 25 ℃ and the rotating speed of 200 rpm.
(4) 2mL of 0.5mol/L Na was added to the reacted solution in the step (3)2And (3) fully reacting the S solution for 6 hours, performing vacuum filtration by using a 0.22 mu m water system filter membrane to obtain filter residues, and finally performing vacuum freeze drying to obtain the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetal load ferrous sulfide composite material prepared by the embodiment is 12m2/g。
The composite material prepared in this example was tested for chromium removal performance in the same manner as in example 1, and the chromium removal efficiency was 49% at 3h, as shown in fig. 3 (a).
Example 6
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) preparing a 200mL hydrochloric acid solution with pH of 4, adding 0.2mmol copper sulfate, and uniformly mixing;
(2) removing dissolved oxygen from the solution in step (1) by nitrogen purging, and sealing by using a film;
(3) adding 1g of reduced iron powder with the granularity of 100 meshes into the solution in the step (2), and fully performing a displacement reaction for 5min in an oil bath shaking table at the temperature of 30 ℃ and the rotating speed of 30 rpm;
(4) 2.2mL of 0.5mol/L Na was added to the reacted solution in step (3)2And (3) carrying out full reaction on the S solution for 1h, carrying out vacuum filtration by using a 0.22 mu m water system filter membrane to obtain filter residue, and finally carrying out vacuum freeze drying to obtain the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetallic load ferrous sulfide composite material prepared by the embodiment is 14m2/g。
The composite material prepared in the embodiment is subjected to chromium removal performance test, the test method is the same as that of the embodiment 1, the chromium removal efficiency is 48% when 3h is measured,
example 7
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) preparing 200mL hydrochloric acid solution with pH of 5.5, adding 0.9mmol copper nitrate, and mixing uniformly;
(2) removing dissolved oxygen from the solution in step (1) by nitrogen purging, and sealing by using a film;
(3) adding 1g of cast iron powder with the granularity of 350 meshes into the solution in the step (2), and fully performing a displacement reaction for 40min in an oil bath shaking table at the temperature of 45 ℃ and the rotating speed of 300 rpm;
(4) 0.7mL of 1.5mol/L Li was added to the reacted solution in the step (3)2S solution is fully reacted for 5 hours and then centrifuged to obtain solid phase, and finally the solid phase is dried in vacuum to obtainTo the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetallic load ferrous sulfide composite material prepared by the embodiment is 14m2/g。
The composite material prepared in the embodiment is subjected to chromium removal performance test, the test method is the same as that of the embodiment 1, the chromium removal efficiency is 46 percent when 3 hours are tested,
example 8
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) preparing a 200mL hydrochloric acid solution with the pH value of 6.9, adding 2.1mmol of copper nitrate, and uniformly mixing;
(2) removing dissolved oxygen from the solution in step (1) by helium flushing, and sealing by using a film;
(3) adding 1g of regenerated iron powder with the granularity of 600 meshes into the solution in the step (2), and fully performing a displacement reaction for 60min in a water bath shaking table with the temperature of 60 ℃ and the rotating speed of 400 rpm;
(4) to the reacted solution in step (3) was added 0.7mL of 2mol/L K2And (4) fully reacting the S solution for 12 hours, performing filter pressing to obtain filter residues, and finally performing freeze drying to obtain the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetal load ferrous sulfide composite material prepared by the embodiment is 17m2/g。
The composite material prepared in the embodiment is subjected to chromium removal performance test, the test method is the same as that of the embodiment 1, the chromium removal efficiency is 45% when 3h is measured,
example 9
The embodiment provides a preparation method of an iron-copper bimetal load ferrous sulfide composite material, which comprises the following steps:
(1) adding 1g of mixed iron powder with the granularity of 325 meshes into 200mL of copper sulfate solution with the concentration of 3.5mmol/L, wherein the mixed iron powder consists of reduced iron powder and regenerated iron powder, and carrying out microwave heating to fully carry out a replacement reaction for 15 min;
(2) adding 1.2m into the solution after the reaction in the step (1)1mol/L of L is Na2And (4) fully reacting the S solution for 9 hours, performing filter pressing to obtain filter residues, and finally performing freeze drying to obtain the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetal load ferrous sulfide composite material prepared by the embodiment is 12m2/g。
The composite material prepared in the embodiment is subjected to chromium removal performance test, the test method is the same as that of the embodiment 1, the chromium removal efficiency is 46 percent when 3 hours are tested,
example 10
Compared with example 1, the difference is only that Na in step (4) is added2The volume of S solution was replaced with 1.8 mL.
The specific surface area of the iron-copper bimetallic load ferrous sulfide composite material prepared by the embodiment is 14m2/g。
The composite material prepared in the embodiment is subjected to chromium removal performance test, the test method is the same as that of the embodiment 1, the chromium removal efficiency is 54 percent when 3 hours are tested,
example 11
Compared with example 1, the difference is only that Na in step (4) is added2The volume of the S solution was replaced with 2.2 mL.
The specific surface area of the iron-copper bimetal load ferrous sulfide composite material prepared by the embodiment is 11m2/g。
The composite material prepared in the embodiment is subjected to chromium removal performance test, the test method is the same as that of the embodiment 1, the chromium removal efficiency is 50% when 3h is measured,
example 12
Compared with example 1, the difference is only that Na in step (4) is added2The volume of S solution was replaced with 2.8 mL.
The specific surface area of the iron-copper bimetal load ferrous sulfide composite material prepared by the embodiment is 10m2/g。
The composite material prepared in the embodiment is subjected to chromium removal performance test, the test method is the same as that of the embodiment 1, the chromium removal efficiency is 45% when 3h is measured,
comparative example 1
Specific method of this comparative example reference exampleExample 2 with the difference that no Na was added in step (4)2And S, carrying out coprecipitation reaction.
Fig. 4 is an SEM image of the surface of the iron-copper bimetal obtained in the present comparative example. The specific surface area of the copper-iron bimetal is 5m2/g。
The iron-copper bimetal obtained in the comparative example is subjected to chromium removal performance test, the test method is the same as that of example 1, and the chromium removal efficiency is 18% when the result is 3 hours.
Comparative example 2
The specific procedure of this comparative example is as in example 2, except that in step (1) the substitution reaction is carried out without adding copper chloride.
FIG. 5 is an SEM image of the surface of the sulfonated iron obtained in the comparative example. The specific surface area of the sulfonated iron is 2m2/g。
The sulfonated iron obtained in the comparative example was subjected to the chromium removal performance test in the same manner as in example 1, and the chromium removal efficiency was 23% at 3 hours, and the concentration change curve is shown in FIG. 3 (a).
Comparative example 3
This comparative example did not have any treatment of the virgin iron powder of example 1.
Fig. 6 is an SEM image of the surface of the original iron powder of this comparative example. The specific surface area of the original iron powder is small and negligible.
The original iron powder of the comparative example was tested for chromium removal performance in the same manner as in example 1, and the chromium removal efficiency was 7% at 3 hours.
Comparative example 4
The comparative example provides a preparation method of an iron-copper bimetallic load ferrous sulfide composite material, which comprises the following steps:
(1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media;
(2) weighing 0.256g of elemental sulfur powder, 2.244g of zero-valent iron powder and 0.512g of zero-valent copper powder, placing the elemental sulfur powder, the 2.244g of zero-valent iron powder and the 0.512g of zero-valent copper powder in a ball milling tank, and filling the tank with nitrogen;
(3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours;
(4) and under the nitrogen atmosphere, separating the prepared iron-copper bimetal load ferrous sulfide composite material from the grinding medium by using a screen to obtain the iron-copper bimetal load ferrous sulfide composite material.
The specific surface area of the iron-copper bimetal load ferrous sulfide composite material prepared by the comparative example is 4m2The chromium removal performance test method is the same as that of the example 1, and the chromium removal efficiency is 14% when the test time is 3 hours.
Evaluation of chromium removal performance of the material:
the materials provided in examples 1-12 and comparative examples 1-4 were tested for chromium removal, as described in example 1, and the results are shown in Table 1.
TABLE 1
The following points can be seen from table 1:
(1) compared with examples 1-4, the specific surface area and the chromium removal efficiency of the composite material obtained in example 5 are lower, because the copper salt is added in a larger amount, the generated copper simple substance is more, and the content of zero-valent iron is relatively lower, so that the activity of the composite material is lower (see fig. 3 (b));
(2) the specific surface area and the chromium removal efficiency of the composite materials obtained in examples 10 and 11 were lower than those of example 1 because of Na in example 102The S is added in a small amount, and the generated ferrous sulfide is less, so that the reaction selectivity of the composite material is poor; EXAMPLE 11 addition of Na2More S is generated, more ferrous sulfide is generated, so that the specific surface area of the composite material is smaller, and the active sites on the surface are reduced;
(3) compared with example 2, the iron-copper bimetal obtained in comparative example 1 has lower specific surface area and chromium removal efficiency, because the iron-copper bimetal of comparative example 1 only forms a tiny primary battery and the reaction selectivity of the material is poor;
(4) the specific surface area and the chromium removal efficiency of the sulfonated iron obtained in comparative example 2 were lower than those of example 2, because the sulfonated iron of comparative example 2 had no minute iron-copper primary cell formed therein and the zero-valent iron had a lower activity;
(5) compared with example 1, the specific surface area of the original iron powder of comparative example 3 is very small and can be ignored; the chromium removal efficiency is low because the activity and the reaction selectivity of the original iron powder are poor;
(6) the composite material obtained in comparative example 4 has lower reactivity compared to example 2, because copper and elemental iron are difficult to combine with each other in a ball milling environment, and cannot form a tiny primary battery.
In conclusion, the iron-copper bimetal loaded ferrous sulfide composite material provided by the invention has the advantages that the iron-copper bimetal forms a tiny primary battery, the reaction activity of zero-valent iron is improved, the ferrous sulfide loaded on the surface of the iron-copper bimetal not only improves the utilization rate of the zero-valent iron and slows down the problem of overhigh passivation speed of the iron-copper bimetal, but also can slow down the water corrosion of the zero-valent iron and improve the reaction selectivity of the material, and the composite material can effectively remove chromium, and the chromium removal efficiency can reach more than 45%. The preparation method provided by the invention combines the preparation process of the iron-copper bimetal with the preparation process of the ferrous sulfide, not only generates the copper simple substance on the surface of the iron simple substance in situ to form a tiny primary battery, accelerates the corrosion of iron, improves the reaction activity of the material, but also recovers the Fe generated in the replacement reaction process2+The method has the advantages of simple preparation steps, economy, effectiveness and good application prospect.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The iron-copper bimetal loaded ferrous sulfide composite material is characterized by comprising iron-copper bimetal and ferrous sulfide loaded on the surface of the iron-copper bimetal, wherein copper in the iron-copper bimetal is loaded on the surface of iron and partially covers the surface of the iron.
2. The composite material according to claim 1, wherein the molar ratio of copper element to iron element in the composite material is (0.01-0.12): 1, preferably (0.04-0.07): 1;
preferably, the molar ratio of the sulfur element to the iron element in the composite material is (0.01-0.12): 1, preferably (0.05-0.08): 1;
preferably, the specific surface area of the composite material is 10-30 m2Preferably 15 to 25 m/g2/g。
3. A method for preparing a composite material according to claim 1 or 2, characterized in that it comprises the following steps:
and mixing the copper salt solution and the iron powder for the first time, and then mixing the mixture and the alkali metal sulfide solution for the second time to obtain the iron-copper bimetal load ferrous sulfide composite material.
4. The method of claim 3, wherein the copper salt solution is mixed with the acidic solution prior to the first mixing;
preferably, the acidic solution comprises an acetic acid buffer solution and/or a hydrochloric acid solution, preferably an acetic acid buffer solution;
preferably, the pH value of the acidic solution is 4-6.9, preferably 5.5-6.5;
preferably, the copper salt solution and the acid solution are mixed to remove dissolved oxygen;
preferably, the method of removing dissolved oxygen comprises purging with nitrogen and/or an inert gas;
preferably, the inert gas comprises argon and/or helium.
5. The method of claim 3 or 4, wherein the copper salt comprises any one of copper chloride, copper sulfate or copper nitrate or a combination of at least two thereof;
preferably, the concentration of copper ions in the copper salt solution is 0.89-10.7 mmol/L, preferably 3.5-6.2 mmol/L;
preferably, the molar ratio of the copper element in the copper salt solution to the iron element in the iron powder is (0.01-0.12): 1, preferably (0.04-0.07): 1;
preferably, the iron powder includes any one or a combination of at least two of reduced iron powder, cast iron powder, or regenerated iron powder;
preferably, the particle size of the iron powder is 100-600 meshes, preferably 325-600 meshes;
preferably, the purity of the iron powder is 80-99%, and preferably 90-98%;
preferably, the time for the primary mixing is 5-60 min, preferably 20-40 min;
preferably, the temperature of the primary mixing is 25-60 ℃, and preferably 25-30 ℃;
preferably, the heating mode of the primary mixing comprises any one or the combination of at least two of direct heating by an electric hot plate, microwave heating, water bath heating or oil bath heating, and preferably water bath heating;
preferably, the primary mixing means comprises stirring;
preferably, the rotation speed of the stirring is 30-400 rpm, preferably 200-300 rpm.
6. The method according to any one of claims 3 to 5, wherein the alkali metal sulfide salt comprises any one or a combination of at least two of sodium sulfide, potassium sulfide or lithium sulfide, preferably sodium sulfide;
preferably, the concentration of the alkali metal sulfide solution is 0.5-2 mol/L, preferably 1-2 mol/L;
preferably, the molar ratio of the sulfur element in the alkali metal sulfide solution to the iron element in the iron powder is (0.01-0.12): 1, preferably (0.05-0.08): 1;
preferably, the time of the secondary mixing is 1-12 hours, and preferably 5-8 hours.
7. The method according to any one of claims 3-6, further comprising: after the second mixing, separation is performed;
preferably, the separation means comprises any one or a combination of at least two of pressure filtration, vacuum filtration or centrifugation, preferably vacuum filtration.
8. The method according to any one of claims 3-7, further comprising: drying the separated solid phase;
preferably, the drying means comprises any one or a combination of at least two of vacuum drying, freeze drying or vacuum freeze drying, preferably vacuum freeze drying.
9. Method according to any of claims 3-8, characterized in that the method comprises the steps of:
(1) adding copper salt into acetic acid-sodium acetate buffer solution with the pH value of 5.5-6.5, and mixing to ensure that the concentration of copper ions is 3.5-6.2 mmol/L;
the copper salt comprises any one or the combination of at least two of copper chloride, copper sulfate or copper nitrate solution;
(2) removing dissolved oxygen from the solution using an inert gas purge and sealing the solution system;
(3) adding 325-600 meshes of iron powder with the purity of 90-98% into the solution system, controlling the molar ratio of copper elements in the copper salt solution to iron elements in the iron powder to be (0.04-0.07): 1, stirring at the temperature of 25-30 ℃ and the rotating speed of 200-300 rpm, heating in a water bath, and reacting for 20-40 min;
the iron powder comprises any one or the combination of at least two of reduced iron powder, cast iron powder or regenerated iron powder;
(4) adding the solution after the reaction in the step (3)Na with a concentration of 1-2 mol/L2And (2) controlling the molar ratio of the sulfur element to the iron element in the iron powder to be (0.05-0.08): 1, reacting for 5-8 h, carrying out vacuum filtration on the mixed solution system by using a 0.22 mu m water system filter membrane to obtain filter residue, and finally carrying out vacuum freeze drying on the filter residue to obtain the iron-copper bimetal load ferrous sulfide composite material.
10. Use of the iron-copper bimetallic supported ferrous sulfide composite material according to claim 1 or 2, characterized in that the composite material is applied in the fields of chromium-containing wastewater treatment and chromium-polluted groundwater remediation.
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