CN110640159B - Micro-nano iron-based powder material, preparation method thereof and application thereof in wastewater treatment - Google Patents
Micro-nano iron-based powder material, preparation method thereof and application thereof in wastewater treatment Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 542
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 216
- 239000000463 material Substances 0.000 title claims abstract description 190
- 239000000843 powder Substances 0.000 title claims abstract description 154
- 238000002360 preparation method Methods 0.000 title description 17
- 238000004065 wastewater treatment Methods 0.000 title description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- 239000000987 azo dye Substances 0.000 claims abstract description 7
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 6
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 claims description 46
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 44
- 229910000765 intermetallic Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 70
- 238000000034 method Methods 0.000 abstract description 31
- 230000000694 effects Effects 0.000 abstract description 29
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 229910000838 Al alloy Inorganic materials 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 72
- 238000004519 manufacturing process Methods 0.000 description 49
- 239000000126 substance Substances 0.000 description 39
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 239000013074 reference sample Substances 0.000 description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000000956 alloy Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 238000004042 decolorization Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 235000013980 iron oxide Nutrition 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
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- B22F1/0007—
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
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- C02F2103/008—Originating from marine vessels, ships and boats, e.g. bilge water or ballast water
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a micro-nano iron-based powder material which comprises a micron-sized iron-based material carrier and nano-sized iron-based material particles positioned on the surface of the micron-sized iron-based material carrier, wherein the surface of the micron-sized iron-based material carrier is provided with gullies with the width of 0.1-0.5 mu m; the size of the micron-sized iron-based material carrier is 50-500 mu m, and the size of the nano-sized iron-based material particles is 2-50 nm. The micro-nano iron-based powder material has a good removing effect on azo dyes, nitrate nitrogen and heavy metals, the micro-nano iron-based powder material directly selects the ferro-aluminum alloy and the sodium hydroxide to react to prepare hydrogen so as to provide hydrogen for ships and aircrafts, and the micro-nano iron-based powder material obtained after the reaction has a good removing effect on the azo dyes, the nitrate nitrogen and the heavy metals, and can be directly used for treating wastewater generated in the running process of the ships and aircrafts.
Description
Technical Field
The invention relates to the field of iron-based composite materials, real-time hydrogen production technology and wastewater treatment, in particular to technology for simultaneously realizing real-time hydrogen production and preparation of a high-activity micro-nano iron-based powder material and application of the micro-nano iron-based powder material in wastewater treatment.
Background
At present, fossil fuels are rapidly consumed, and the use of fossil fuels causes serious environmental pollution. The concept of hydrogen economy has been proposed as early as the 70's of the 19 th century, aiming to replace the existing petroleum economy systems with clean hydrogen energy on a large scale. The proportion of hydrogen energy in the energy structure in 2050 is expected to reach more than 18 percent, so that 60 hundred million tons of greenhouse gas emission per year can be reduced, and the temperature of global warming rise is controlled within 2 ℃. However, at present, more than 95% of hydrogen is prepared by depending on fossil fuel, and a large amount of greenhouse gas is emitted while hydrogen is generated, which violates the original purpose of hydrogen use and the concept of clean production; in addition, the difficult nature of compressed storage of hydrogen makes it inconvenient to use in special environments (e.g., closed environments such as ships, aircraft, etc.). Therefore, the development of hydrogen clean production technology and real-time hydrogen production technology is crucial to the utilization and development of future hydrogen energy.
The environmental pollution problem is becoming more severe. Zero-valent iron (ZVI) has been used as an adsorbent and reductant in the treatment of chlorinated hydrocarbons, heavy metals, dyes, explosive pollutants, toxic anions and radioactive pollutants in water. Nano zero-valent iron (nZVI) has been widely studied and used because of its large specific surface area and high treatment efficiency. Three conventional methods for obtaining nZVI, namely liquid phase reduction of Fe2+/Fe3+Ball milling and reduction of iron oxide. Currently most commercial nZVI uses NaBH4The liquid phase reduction method is used for preparing the nZVI, however, the cost (over 200 dollars/kg) for preparing the nZVI is greatly increased by using NaBH4 liquid phase reduction, and the nZVI has the defects of easy agglomeration, poor liquidity and the like, so that the nZVI is difficult to achieve the expected effect in practical application. Indeed, the singleness of current ZVI manufacturing processes limits the physicochemical properties of ZVI products, which in turn affects the resistance of ZVI products to certain influencing factors (such as pH) when removing contaminants. The performance of the nZVI composite material prepared by the stabilizing technologies such as vulcanization, loading and the like can be improved, but in order to fundamentally solve the defects of ZVI and nZVI in practical application, a new ZVI preparation technology needs to be developed.
The present invention has been made to solve the above problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention firstly provides a technology capable of simultaneously realizing real-time hydrogen production and preparation of a high-activity micro-nano iron-based powder material, and secondly provides an application of treating wastewater containing nitrate nitrogen, azo dyes or heavy metals.
The invention provides a micro-nano iron-based powder material, which comprises a micron-sized iron-based material carrier and nano-sized iron-based material particles positioned on the surface of the micron-sized iron-based material carrier, wherein the surface of the micron-sized iron-based material carrier is provided with gullies.
In a preferred embodiment of the first aspect of the present invention, the widths of the ravines are 0.1-0.5 μm.
In a preferred embodiment of the first aspect of the present invention, there are 3 to 10 ravines per 10 μm in a direction perpendicular to the ravines.
In a preferred embodiment of the first aspect of the present invention, the size of the carrier of the iron-based material is 50 to 500 μm, and the size of the particles of the iron-based material is 2 to 50 nm.
Wherein the BET specific surface area of the micro-nano iron-based powder material is 2-70 m2/g。
In a preferred embodiment of the first aspect of the present invention, the micro-nano iron-based powder material includes elementary iron, elementary aluminum, and iron oxide or intermetallic compound, and the iron oxide is Fe3O4The intermetallic compound is selected from but not limited to Al13Fe4、Al2Fe or Al5Fe2The intermetallic compounds with different iron contents in the aluminum-iron alloy are different in types, but the aluminum-iron alloy is suitable for the invention, and the material becomes a micro-nano iron-based powder material. Most preferably, the micro-nano iron-based powder material only comprises iron simple substance, and at this time, the iron-based powder material is called micro-nano zero-valent iron (ZVI).
In a preferred embodiment of the first aspect of the present invention, the micro-nano iron-based powder material is stored in oxygen-free ethanol.
The second aspect of the invention provides a preparation method of the micro-nano iron-based powder material, which comprises the steps of putting an aluminum-iron alloy into a sodium hydroxide solution, stirring and reacting to obtain the micro-nano iron-based powder material, wherein the reaction temperature is not limited, the concentration of sodium hydroxide is 0.5-5 mol/L, and the reaction time is 10-60 min.
In a preferred embodiment of the second aspect of the present invention, the aluminum-iron alloy has a size of 20 to 200 mesh.
The preparation method of the aluminum-iron alloy comprises the following steps: adding simple substance Al and simple substance Fe into a smelting furnace, heating the smelting furnace in vacuum to melt the simple substance Al and the simple substance Fe into a whole, preparing an aluminum-iron alloy ingot through a heat preservation process and a cooling process, crushing the aluminum-iron alloy ingot through a lathe, and then screening alloy powder with the mesh number of 20-200 meshes by using a standard screen to obtain the aluminum-iron alloy.
The method comprises the following steps of putting an aluminum-iron alloy into a sodium hydroxide solution, stirring and reacting to generate hydrogen, when the percentage of actual hydrogen production to theoretical hydrogen production is 100%, completely consuming aluminum in the aluminum-iron alloy, wherein the micro-nano iron-based powder material only comprises iron simple substance, at the moment, the micro-nano iron-based powder material is called micro-nano zero-valent iron (ZVI), and iron-based material carriers and iron-based material particles are iron simple substances; when the actual hydrogen production accounts for less than 100% of the theoretical hydrogen production, the micro-nano iron-based powder material comprises an iron simple substance, an undisluked aluminum simple substance and an undisluked Al intermetallic compound (Al)13Fe4、Al2Fe、Al5Fe2). If the micro-nano zero-valent iron obtained when the actual hydrogen production accounts for 100 percent of the theoretical hydrogen production is placed in the air, part of iron simple substances on the surface of the micro-nano zero-valent iron are oxidized into iron oxides (Fe) by oxygen3O4) At the moment, the micro-nano iron-based powder material comprises iron simple substance and Fe3O4。
In a preferred embodiment of the second aspect of the present invention, the mass ratio of the elemental Al to the elemental Fe is 1: 1 to 9: 1.
the third aspect of the invention provides an application of the micro-nano iron-based powder material in wastewater treatment, wherein the wastewater is wastewater containing azo dyes, nitrate nitrogen and heavy metals, can be wastewater generated in the running process of ships and aircrafts, and is added with the micro-nano iron-based powder material for reaction.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention prepares a micro-nano iron-based powder material, which comprises a micron-sized iron-based material carrier and nano-sized iron-based material particles positioned on the surface of the iron-based material carrier, wherein the surface of the micron-sized iron-based material carrier is provided with a gully with the width of 0.1-0.5 mu m; the size of the iron-based material carrier is 50-500 mu m, and the iron-based material particles are formed by stacking iron-based material particles with the size of 2-50 nm.
2. In the process of preparing the micro-nano iron-based powder material, hydrogen can be generated simultaneously, the hydrogen is 20-40 meshes at the normal temperature of 25 ℃, and the mass ratio of simple substance Al to simple substance Fe is 4: the hydrogen production rate of 4Al-Fe of 1 in 2mol/LNaOH solution reaches 41.3 ml/(g.min), and the hydrogen production rate in 5mol/LNaOH solution reaches 82.1 ml/(g.min). As the hydrogen production raw materials in the reaction only comprise sodium hydroxide solution and aluminum-iron alloy which are convenient to carry, the method can be used for providing hydrogen sources for ships and aircrafts, and solves the problem that the hydrogen is inconvenient to use in special environments (such as closed environments of ships, aircrafts and the like) due to the difficult compression and storage property of the hydrogen in the prior art.
3. The micro-nano iron-based powder material prepared by the invention has NO effect on toxic anions in wastewater3 -Has good removal effect, and the adding amount of the micro-nano zero-valent iron is 1g/L and 50mgN/LNO under the conditions that the pH is neutral and the reaction temperature is 25 DEG C3 -The removal rate reaches 72% in 30min, the nitrogen selectivity of the product reaches 40%, under the same condition, the removal rate of the nano zero-valent iron prepared by the liquid phase reduction method is 50% in 30min, the nitrogen selectivity of the product is 0%, and the removal rate of the reduced iron powder prepared by the method for reducing iron oxide is 0% in 30 min.
4. The micro-nano iron-based powder material prepared by the invention has good removal effect on AO7 and Cr (VI) in wastewater, the removal effect of a sample 1 of the micro-nano iron-based powder material prepared by the invention on AO7 and Cr (VI) is far higher than that of reduced iron powder, compared with nano zero-valent iron, the micro-nano iron-based powder material prepared by the invention has obviously better removal effect on nitrate nitrogen than that of the nano zero-valent iron, and after the reaction is carried out for 10 minutes under the same condition,NO when treated with nano zero-valent iron3 -The removal rate is 16.9 percent, and NO is generated when the sample 1 of the micro-nano iron-based powder material is treated3 -The removal rate has been as high as 57.08%. For the removal of the azo dye AO7, although the removal effect of the micro-nano iron-based powder material sample 1 on AO7 is slightly lower than that of nano zero-valent iron in the initial reaction stage (the first ten minutes), the removal rate of the two on AO7 is close to 100% after the reaction is continued for twenty minutes. Similarly, for the removal of cr (vi), although the removal effect of the micro-nano iron-based powder material sample 1 on cr (vi) is not as good as that of nano zero-valent iron at the beginning of the reaction, the removal rate of cr (vi) can also reach 90.41% when the micro-nano iron-based powder material sample 1 is used after the reaction is continued for thirty minutes. Therefore, the removal effect of the micro-nano iron-based powder material prepared by the invention on AO7 and Cr (VI) is slightly lower than that of nano zero-valent iron, but the cost of the nZVI prepared by the liquid phase reduction method is very high and exceeds $ 200/kg, on the other hand, the nZVI has the defects of easy agglomeration, poor flowability and the like due to the nano-scale particle size, and the effect of the nZVI in practical application is difficult to achieve the expectation due to the problems. In comparison, in the initial stage of the reaction, the removal effect of the micro-nano iron-based powder material prepared by the invention on AO7 and Cr (VI) is slightly lower than that of nano zero-valent iron, but after the reaction time is prolonged, the removal rate of AO7 and Cr (VI) can also reach more than 90 percent, and the micro-nano iron-based powder material prepared by the invention has the advantages of simple preparation method and low cost, and is very suitable for practical application. On the other hand, in the process of preparing the micro-nano iron-based powder material sample 1, hydrogen can be simultaneously produced, and the hydrogen production rate reaches 41.3 ml/(g.min).
5. The micro-nano iron-based powder material prepared by the invention can be suitable for wastewater treatment in a wider pH value range, and the decolorization rate of 500mg/L acid orange 7 is more than 88% in 30min under the condition of initial pH of 3-11.
6. The hydrogen production performance in the preparation process of the micro-nano zero-valent iron is reduced along with the reduction of the particle size of the aluminum-iron alloy, because the iron content in the aluminum-iron alloy with small particle size is higher in the crushing process of the alloy, so that the actual hydrogen production is lower than the theoretical value. Another one isIn the aspect, the different particle sizes of the aluminum-iron alloy have NO great influence on the appearance and components of the micro-nano zero-valent iron product, and further the micro-nano zero-valent iron can not influence the AO7 and NO3 -And Cr (VI) removal effect. Therefore, the aluminum-iron alloy with larger grain diameter can be directly selected and used for reacting with sodium hydroxide to prepare hydrogen, hydrogen is provided for ships and aircrafts, the micro-nano zero-valent iron obtained after reaction can be directly used for treating wastewater generated in the running process of the ships and aircrafts, the difficulty of hydrogen production in the special environment of the ships and aircrafts is solved, and the problem that the wastewater generated in the running process of the ships and aircrafts is difficult to treat is also solved.
Drawings
FIG. 1 is an SEM image of a micro-nano iron-based powder material sample 1 in example 1 of the present invention;
FIG. 2 is an XRD (X-ray diffraction) diagram of a micro-nano iron-based powder material sample 1 in embodiment 1 of the invention;
FIG. 3 is an XPS chart of a micro-nano iron-based powder material sample 1 in example 1 of the present invention;
FIG. 4 is a TEM image of a micro-nano iron-based powder material sample 1 in example 1 of the present invention at a scale of 100 nm;
FIG. 5 is a TEM image of a micro-nano iron-based powder material sample 1 in example 1 of the present invention at a scale of 10 nm;
FIG. 6 is a TEM image of a micro-nano iron-based powder material sample 1 in example 1 of the present invention at a scale of 2 nm;
FIG. 7 is an SEM image of a micro-nano iron-based powder material sample 5 in example 5 of the present invention;
FIG. 8 is an XRD (X-ray diffraction) diagram of a micro-nano iron-based powder material sample 5 in embodiment 5 of the invention;
FIG. 9 is an SEM image of a micro-nano iron-based powder material sample 7 in example 7 of the present invention;
FIG. 10 is an XRD (X-ray diffraction) diagram of a micro-nano iron-based powder material sample 7 in example 7 of the present invention;
Detailed Description
The invention is described in further detail below with reference to the figures and examples, but it should be understood that the following specific examples are only illustrative of the invention and do not limit the scope of the invention in any way.
Comparative example 1
In the comparison example, a nanometer zero-valent iron comparison sample 1 is prepared by a liquid phase reduction method:
with ferric chloride (FeCl) hexahydrate3·6H2O) as a precursor, and 50mL FeCl prepared by oxygen-free deionized water3Solution (0.08mol/L) with 50mL NaBH4Mixing the solutions (0.24mol/L), magnetically stirring for 1h under the condition of introducing argon, and repeatedly washing the obtained product with oxygen-free deionized water to obtain a nano zero-valent iron reference sample 1.
Comparative example 2
In this comparative example, reduced iron powder (analytical grade) purchased from Fochen chemical reagent works of Tianjin was selected as the reduced iron powder comparative sample 2.
Example 1
In the embodiment, firstly, a micro-nano iron-based powder material sample 1 is prepared:
(1) adding simple substance Al and simple substance Fe into a smelting furnace, wherein the mass ratio of the simple substance Al to the simple substance Fe is 4:1, heating the smelting furnace in vacuum to melt the simple substance Al and the simple substance Fe into a whole, then preparing an aluminum-iron alloy ingot through a heat preservation process and a cooling process, crushing the aluminum-iron alloy ingot through a lathe, and then screening out alloy powder with the mesh number of 20-40 by using a standard sieve to obtain the aluminum-iron alloy 4Al-Fe (20-40 meshes), wherein 4Al-Fe represents that the mass ratio of the simple substance Al to the simple substance Fe is 4: 1;
(2) adding 1g of aluminum-iron alloy 4Al-Fe (20-40 meshes) prepared in the step (1) into 100mL of 2mol/L NaOH solution at the normal temperature of 25 ℃, stirring and reacting to produce hydrogen, measuring the hydrogen production rate to be 41.3 mL/(g.min), after stirring and reacting for 20min, calculating the hydrogen production rate to be 100%, collecting the residual solid product to obtain a micro-nano iron-based powder material sample 1, and immediately placing the micro-nano iron-based powder material sample in an oxygen-free ethanol solution for storage.
The hydrogen production rate is the percentage of the actual hydrogen production relative to the theoretical hydrogen production and is calculated as follows:
wherein a is the adding amount (g) of the alloy, and b is the mass fraction of aluminum in the aluminum-iron alloy.
The hydrogen production rate is the hydrogen production variable (ml/(g min)) of unit mass of alloy in unit time, and the calculation method is as follows:
wherein a is the adding amount (g) of the alloy, and t is the time (min) for consuming a g alloy to produce hydrogen.
Examples 2 to 7
Examples 2 to 7 are preparation of micro-nano iron-based powder material samples 2 to 10, the preparation method is the same as example 1, and only the mass ratio of the simple substance Al to the simple substance Fe, the particle size of the aluminum-iron alloy or the reaction time are different in the preparation conditions, wherein the preparation conditions of the micro-nano iron-based powder material samples in examples 1 to 7 are shown in table 1 below:
example 8
The embodiment respectively represents a micro-nano iron-based powder material sample 1 and a micro-nano iron-based powder material sample 6, and the method specifically comprises the following steps:
XRD, SEM, TEM and XPS detection is carried out on the obtained micro-nano iron-based powder material sample 1, and the result is as follows:
wherein, fig. 1 is a SEM image of a micro-nano iron-based powder material sample 1, fig. 2 is an XRD image of the micro-nano iron-based powder material sample 1, fig. 3 is an XPS image of the micro-nano iron-based powder material sample 1, and fig. 4, 5, 6 are TEM images of the micro-nano iron-based powder material sample 1 at different scales (100nm, 10nm, 2nm), respectively.
The etching product after complete hydrogen production is further characterized, and the XPS analysis result of the micro-area on the surface of the micro-nano iron-based powder material sample 1 is shown asAs shown in FIG. 3, peak "1" and peak "2" are associated with Fe, respectively3+At Fe2p3/2The peaks of the orbits coincide, peak "3" being Fe2p3/2Orbital satellite peak, peak "4" and Fe2+At Fe2p1/2The peaks of the tracks are coincident, which shows that Fe exists on the surface of the micro-nano iron-based powder material sample 13O4This is because after the micro-nano iron-based powder material sample 1 is taken out from the alkali solution, in the above detection process, the surface Fe is rapidly oxidized in the air, and needle-like Fe is formed on the surface3O4But still keeps the original gully shape. Therefore, the micro-nano zero-valent iron prepared by the method is immediately put in the oxygen-free ethanol for storage after being taken out of the alkali liquor. The TEM characterization results are shown in fig. 4, 5 and 6, and the lattice fringe spacing inside the micro-nano iron-based powder material sample 1 is consistent with the lattice spacing of the Fe (110) crystal face, which indicates that the inside of the micro-nano iron-based powder material sample 1 is elemental Fe. According to XRD and SEM results and TEM results after adjusting magnification, the micro-nano iron-based powder material sample 1 consists of two parts, namely a blocky product decomposed after being etched by alkali liquor, namely the micron-sized iron-based material carrier, and nano-sized iron-based material particles agglomerated on the surface of the micron-sized iron-based material carrier, wherein the size of the iron-based material particles is 50-500 mu m, and the size of the nano-sized iron-based material particles is 2-50 nm. The micron-sized iron-based material carrier and the nano-sized iron-based material particles respectively correspond to an iron simple substance with gully morphology left after an aluminum simple substance in the aluminum-iron alloy is dissolved out and an intermetallic compound (Al) in the aluminum-iron alloy13Fe4、Al2Fe、Al5Fe2) The Al in (b) dissolves out the remaining Fe.
Then, XRD and SEM detection is carried out on the obtained micro-nano iron-based powder material 5, and the result is as follows:
wherein, fig. 7 is a SEM image of the micro-nano iron-based powder material 5, and fig. 8 is an XRD image of the micro-nano iron-based powder material 5. As can be seen from the SEM image, even the micro/nano iron-based powder material 5 obtained at a hydrogen production rate of 25% still includes a micron-sized iron-based material carrier having a gully morphology and nano-sized iron-based material particles on the surface of the micron-sized iron-based material carrier. Since the aluminum-iron alloyAluminum in the powder is not completely dissolved out, and the micro-nano iron-based powder material 5 comprises an aluminum simple substance, an iron simple substance and an intermetallic compound Al13Fe4And XRD patterns also verify this.
And finally, carrying out XRD and SEM detection on the obtained micro-nano iron-based powder material 7, wherein the result is as follows:
wherein, fig. 9 is a SEM image of the micro-nano iron-based powder material 7, and fig. 10 is an XRD image of the micro-nano iron-based powder material 7. As can be seen from the SEM image, even if the micro-nano iron-based powder material 7 obtained when the hydrogen production rate is 75% includes a micron-sized iron-based material carrier having a gully morphology and nano-sized iron-based material particles on the surface of the micron-sized iron-based material carrier, and the longer the reaction time of the aluminum-iron alloy and the sodium hydroxide is, that is, the higher the hydrogen production rate is, the more obvious the gully is on the micron-sized iron-based material carrier in the obtained micro-nano iron-based powder material. Because aluminum in the aluminum-iron alloy is not completely dissolved out, the micro-nano iron-based powder material 7 should comprise an aluminum simple substance, an iron simple substance and an intermetallic compound Al13Fe4And XRD patterns also verify this.
In summary, when the actual hydrogen production amount is equal to the theoretical hydrogen production amount, that is, the hydrogen production rate is equal to 100%, aluminum in the aluminum-iron alloy is completely consumed, the micro-nano iron-based powder material only includes a simple substance of iron, at this time, the micro-nano iron-based powder material is called micro-nano zero-valent iron (ZVI), both the iron-based material carrier and the iron-based material particles are the simple substance of iron, and the micro-scale iron-based material carrier and the nano-scale iron-based material particles respectively correspond to the simple substance of iron with a gully morphology and the intermetallic compound (Al) in the aluminum-iron alloy (the iron simple substance with a gull13Fe4、Al2Fe、Al5Fe2) Dissolving out residual Fe from Al in the alloy; when the actual hydrogen production accounts for less than 100% of the theoretical hydrogen production, the micro-nano iron-based powder material comprises an iron simple substance, an undisluked aluminum simple substance and an undisluked Al intermetallic compound (Al)13Fe4、Al2Fe、Al5Fe2). If the micro-nano zero-valent iron obtained when the percentage of the actual hydrogen production to the theoretical hydrogen production is 100 percent is placed in the air, the micro-nano zero-valent iron is micro-scalePart of iron simple substance on the surface of the nano zero-valent iron is oxidized into iron oxide (Fe) by oxygen3O4) At the moment, the micro-nano iron-based powder material comprises iron simple substance and Fe3O4。
In addition, BET characterization is performed on the nano zero-valent iron reference sample 1, the reduced iron powder reference sample 2 and the micro-nano iron-based powder material sample prepared by the invention, and the result is shown in table 2 below:
TABLE 2 BET specific surface areas of the different samples
| Sample (I) | BET specific surface area (m)2/g) |
| Nano zero-valent |
100 |
| Reduced iron |
0.25 |
| Micro-nano iron-based |
61 |
| Micro-nano iron-based |
70 |
| Micro-nano iron-based |
58 |
| Micro-nano iron-based powder material sample 4 | 54 |
| Micro-nano iron |
3 |
| Micro-nano iron-based powder material sample 6 | 2 |
| Micro-nano iron-based powder material sample 7 | 4 |
As can be seen from Table 2, the specific surface area of the micro-nano iron-based powder material sample is 2-70 m2g, the specific surface area of the micro-nano iron-based powder material sample of the product can be influenced by the mass ratio of the simple substance Al to the simple substance iron in the aluminum-iron alloy, the concentration of sodium hydroxide, the particle size of the aluminum-iron alloy or whether hydrogen is completely generated or not, it can be seen from table 2 that the specific surface area of the micro-nano iron-based powder material samples 1-4 is significantly higher than that of the micro-nano iron-based powder material samples 5-7, since the examples 1-4 are close to complete hydrogen production, the specific gully morphology of the micro-nano iron-based powder material sample is a main reason for influencing the specific surface area of the product, the process of producing hydrogen by reaction (the process of forming the micro-nano iron-based powder material sample) is a process of exposing a special appearance, a special gully appearance is formed, the specific surface area is increased, and the specific surface area of the micro-nano zero-valent iron is the largest under the same preparation conditions. Wherein, the specific surface area of the micro-nano iron-based powder material sample 1 can reach 61m2(ii) in terms of/g. The specific surface area of the nano zero-valent iron reference sample 1 prepared by adopting a liquid phase reduction method is 100m2(g), the specific surface area of reduced iron powder comparative sample 2 prepared by the reduced iron oxide method was only 0.25m2/g。
Example 9
In this embodiment, the removal effect of the ten samples, namely the nano zero-valent iron reference sample 1, the reduced iron powder reference sample 2 and the micro-nano iron-based powder material samples 1 to 7, on acid orange 7(AO7) is respectively examined, and the specific evaluation method is as follows:
the iron-based material was placed in 200mL of 200mg/LAO7 solution and magnetically stirred (300r/min) for contaminant removal. Taking water samples when the reaction is carried out for 1, 3, 5, 10, 15, 20 and 30min respectively, and filtering the water samples by using a 0.22 mu m microporous filter membrane. And (3) measuring the absorbance of the filtered water sample at 485nm by using a double-beam ultraviolet-visible spectrophotometer, and comparing the absorbance with a standard curve to obtain the concentration of AO7 in the solution when the reaction is carried out for 30 min.
Wherein, the AO7 decoloration ratio is calculated as shown in formula (1), C0The initial concentration of AO7, and C the concentration of AO7 at a time during the experiment.
The above evaluation results are shown in Table 3:
TABLE 3 decolorization ratio of different samples to AO7
Example 10
In this example, ten samples of a nano zero-valent iron reference sample 1, a reduced iron powder reference sample 2 and micro/nano iron-based powder material samples 1 to 7 were examined for NO3 -The specific evaluation method of (2) is as follows:
the iron-based material was put into a 50mgN/L potassium nitrate solution, and magnetically stirred (300r/min) to conduct a contaminant removal experiment. Sampling at 1, 3, 5, 10, 15, 20 and 30min respectively, filtering the water sample with a 0.22-micron microporous filter membrane, measuring absorbance of the filtered water sample at 543nm by using a double-beam ultraviolet-visible spectrophotometer, and comparing with a standard curve to calculate the concentration of nitrite nitrogen; measuring absorbance of the filtered water sample at 220nm by using a double-beam ultraviolet-visible spectrophotometer, comparing with a standard curve, and calculating the concentration of nitrate and nitrogen; the ammonia nitrogen concentration was then measured using ion chromatography.
Wherein the nitrate removal product N2The formula (2) is shown in the specification, and C is concentration.
NO3 -The removal rate is calculated as shown in formula (3), C0The initial concentration of AO7, and C the time of NO3 -The concentration of (c).
The selectivity of the product nitrogen is the nitrogen yield and NO3 -The ratio of the consumption is calculated as shown in formula (4).
The above evaluation results are shown in Table 4:
TABLE 4 different sample pairs NO3 -Removal rate of
Example 11
In this embodiment, the removing effect of ten samples, namely a nano zero-valent iron reference sample 1, a reduced iron powder reference sample 2 and micro-nano iron-based powder material samples 1 to 7, on cr (vi) is respectively considered, and the specific evaluation method is as follows:
the iron-based material is put into 20mg Cr/L potassium dichromate solution and is magnetically stirred (300r/min) to carry out the pollutant removal experiment. Sampling at 1, 3, 5, 10, 15, 20, and 30min respectively, filtering with 0.22 μm microporous membrane, and filtering with 2.5% KNO3Diluted 5 times, and the total Cr concentration was measured by ICP-OES.
In the experimental process, Cr (VI) is converted into insoluble Cr (III) precipitate to be removed, so that the removal rate of Cr (VI) is calculated as shown in a formula (5), and C0Is the initial Cr (VI) concentration, and C is the total Cr concentration at a certain time in the experimental process.
The above evaluation results are shown in Table 5:
TABLE 5 removal of Cr (VI) from various samples
Example 12
By comparing the nanometer zero-valent iron reference sample 1, the reduced iron powder reference sample 2 and the micro-nano iron-based powder material sample 1 in tables 3-5, the micro-nano iron-based powder material sample 1 prepared by the invention can be known to be AO7 and NO3 -Compared with the nanometer zero-valent iron, the micro-nano iron-based powder material sample 1 prepared by the invention has the removal effect far higher than that of the reduced iron powder, and the removal effect of Cr (VI) is obviously better than that of the nanometer zero-valent iron, under the same condition, after the reaction is carried out for 10 minutes, when the nanometer zero-valent iron is used for treatment, NO is added3 -The removal rate is 16.9 percent, and NO is generated when the sample 1 of the micro-nano iron-based powder material is treated3 -The removal rate has been as high as 57.08%. For the removal of the azo dye AO7, although the removal effect of the micro-nano iron-based powder material sample 1 on AO7 is slightly lower than that of nano zero-valent iron in the initial reaction stage (the first ten minutes), the removal rate of the two on AO7 is close to 100% after the reaction is continued for twenty minutes. Similarly, for the removal of cr (vi), although the removal effect of the micro-nano iron-based powder material sample 1 on cr (vi) is not as good as that of nano zero-valent iron at the beginning of the reaction, the removal rate of cr (vi) can also reach 90.41% when the micro-nano iron-based powder material sample 1 is used after the reaction is continued for thirty minutes. Therefore, the removal effect of the micro-nano iron-based powder material prepared by the invention on AO7 and Cr (VI) is slightly lower than that of nano zero-valent iron, but the cost of the nZVI prepared by the liquid phase reduction method is very high and exceeds $ 200/kg, on the other hand, the nZVI has the defects of easy agglomeration, poor flowability and the like due to the nano-scale particle size, and the problems lead the effect of the nZVI in practical applicationIt is difficult to achieve the expectation. In comparison, in the initial stage of the reaction, the removal effect of the micro-nano iron-based powder material prepared by the invention on AO7 and Cr (VI) is slightly lower than that of nano zero-valent iron, but after the reaction time is prolonged, the removal rate of AO7 and Cr (VI) can also reach 90%, and the micro-nano iron-based powder material prepared by the invention has the advantages of simple preparation method and low cost, and is very suitable for practical application. On the other hand, in the process of preparing the micro-nano iron-based powder material sample 1, hydrogen can be simultaneously produced, and the hydrogen production rate reaches 41.3 ml/(g.min).
Comparing the micro-nano iron-based powder material samples 1-3 in tables 3-5, it can be seen that the hydrogen production performance in the preparation process of the micro-nano iron-based powder material is reduced along with the increase of the iron content in the aluminum-iron alloy, and the hydrogen production rates of 20-40 mesh 9Al-Fe, 4Al-Fe and Al-Fe in 2mol/LNaOH are 100%, 92% and 29% respectively. On the other hand, when the aluminum-iron alloy with different iron contents is used for completely producing hydrogen, the micro-nano iron-based powder material pair AO7 and NO are prepared3 -And Cr (VI) removal effect had no effect.
By comparing the micro-nano iron-based powder material sample 1 and the micro-nano iron-based powder material sample 4 in tables 3-5, the hydrogen production performance in the preparation process of the micro-nano iron-based powder material is reduced along with the reduction of the particle size of the aluminum-iron alloy, however, the difference of the particle size of the aluminum-iron alloy does not have great influence on the appearance and components of the micro-nano iron-based powder material, and further the micro-nano iron-based powder material can not influence AO7 and NO3 -And Cr (VI) removal effect. Therefore, when the aluminum-iron alloy hydrogen production is used for providing hydrogen energy for the field of ships and aircrafts, and then the micro-nano iron-based powder material obtained during the hydrogen production is used for treating wastewater generated during the operation of the ships and aircrafts, the aluminum-iron alloy with larger grain diameter can be directly selected as a raw material in consideration of inconvenient storage and use of the aluminum-iron alloy powder with small grain diameter.
By comparing the micro-nano iron-based powder material sample 1, the micro-nano iron-based powder material sample 5, the micro-nano iron-based powder material sample 6 and the micro-nano iron-based powder material sample 7 in tables 3 to 5, the stirring of the aluminum-iron alloy in the alkali liquor is controlled according to the actual hydrogen production rateTime. Solid products obtained by stirring aluminum-iron alloy in alkali liquor and used for respectively removing acid orange 7 and NO3 -The effect of Cr (VI) and Cr (VI) is improved along with the process of hydrogen production of the aluminum-iron alloy, when the aluminum-iron alloy completely produces hydrogen in alkali liquor, namely the hydrogen production rate is 100 percent, the obtained micro-nano iron-based powder material is used for treating acid orange 7 and NO3 -And Cr (VI), if the hydrogen production is finished, the micro-nano iron-based powder material is continuously placed in alkali liquor or directly placed in the air, and Fe on the surface of the micro-nano iron-based powder material is oxidized into Fe3O4Its ability to remove contaminants will gradually decline.
Example 13
In this embodiment, with reference to the evaluation method of example 9, under the conditions of pH 3, pH 5, pH 7, pH 9, and pH 11, respectively, a micro-nano iron-based powder material sample 1 is used to perform a decolorization reaction on 500mg/L acid orange 7, a pH value of the acid orange 7 is examined, a water sample is taken at 30min, the water sample is filtered by a 0.22 μm microporous filter membrane, absorbance of the filtered water sample is measured at 485nm by a dual-beam ultraviolet-visible spectrophotometer, and the absorbance is compared with a standard curve to obtain the AO7 concentration in a solution in each time period, and the decolorization rate in each time period is calculated, with the results as shown in table 6 below:
TABLE 6 decolorization ratio of micro-nano iron-based powder material to AO7 solutions with different pH values
From table 6, it can be found that the higher the pH of the initial acid orange 7 is, the lower the decolorization rate of the acid orange 7 is, but after the reaction is carried out for 30min, the decolorization rates of the acid orange 7 under various pH conditions are gradually similar, which may be because the micro-nano iron-based powder material of the present invention has a larger specific surface area, and the high adsorbability of the ultra-high activity nano iron makes up for the deficiency of the reducing power caused by the increase of the initial pH, and in summary, the decolorization rate of 500mg/L of acid orange 7 is above 88% at 30min under the condition that the initial pH of the acid orange 7 is 3-11.
Claims (7)
1. The micro-nano iron-based powder material is characterized by comprising a micro-scale iron-based material carrier and nano-scale iron-based material particles positioned on the surface of the micro-scale iron-based material carrier, wherein the surface of the micro-scale iron-based material carrier is provided with gullies;
the size of the micron-sized iron-based material carrier is 50-500 mu m; the size of the nano-scale iron-based material particles is 2-50 nm;
3-10 ravines are arranged along the direction vertical to the ravines every 10 mu m;
putting an aluminum-iron alloy into a sodium hydroxide solution, and stirring for reaction to obtain the micro-nano iron-based powder material, wherein the reaction temperature is not limited, the concentration of sodium hydroxide is 0.5-5 mol/L, and the reaction time is 10-60 min;
the particle size of the aluminum-iron alloy is 20-40 meshes or 180-200 meshes; the adding amount of the aluminum-iron alloy in the sodium hydroxide solution is 0.01 g/ml.
2. The micro-nano iron-based powder material of claim 1, wherein the widths of the ravines are 0.1-0.5 μm.
3. The micro-nano iron-based powder material of claim 1, wherein the corrugations extend in the same direction or are staggered with respect to each other.
4. The micro-nano iron-based powder material of claim 1, wherein the micro-nano iron-based material carrier comprises elemental iron, the nano-scale iron-based material particles comprise Fe dissolved out of Al in intermetallic compounds in aluminum-iron alloy, and the intermetallic compounds are selected from Al13Fe4、Al2Fe or Al5Fe2。
5. The micro-nano iron-based powder material of claim 4, wherein the micro-nano iron-based powder material only comprises iron.
6. The micro-nano iron-based powder material of claim 1, wherein the mass ratio of Al to Fe in the aluminum-iron alloy is 1: 1 to 9: 1.
7. the application of the micro-nano iron-based powder material disclosed in claim 1 in treating wastewater containing azo dyes, nitrate nitrogen and heavy metals.
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| CN101269315B (en) * | 2008-05-12 | 2011-08-31 | 河北理工大学 | Modified spherical sponge iron for wastewater treatment and preparation method |
| CN101456077B (en) * | 2009-01-09 | 2011-01-26 | 天津大学 | Preparation method of nano zero-valence iron base function macroscopic ball |
| CN104190916B (en) * | 2014-08-27 | 2017-01-11 | 厦门大学 | Oxidation resisting hydrolysis hydrogen generation composite powder and preparation method thereof |
| CN104827028B (en) * | 2015-04-15 | 2016-04-20 | 刘骁勇 | Composite nano zero-valent iron particle |
| US10865464B2 (en) * | 2016-11-16 | 2020-12-15 | Hrl Laboratories, Llc | Materials and methods for producing metal nanocomposites, and metal nanocomposites obtained therefrom |
| CN106925772B (en) * | 2017-04-17 | 2018-08-14 | 中国工程物理研究院化工材料研究所 | The preparation method of micro-/ nano composite material of core-shell structure |
| CN108746604A (en) * | 2018-06-26 | 2018-11-06 | 厦门理工学院 | A kind of air-stable type nano zero valence iron and its preparation method and application |
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