CN115522073B - Modified hematite material and preparation method and application thereof - Google Patents
Modified hematite material and preparation method and application thereof Download PDFInfo
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- CN115522073B CN115522073B CN202210962017.XA CN202210962017A CN115522073B CN 115522073 B CN115522073 B CN 115522073B CN 202210962017 A CN202210962017 A CN 202210962017A CN 115522073 B CN115522073 B CN 115522073B
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- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000000463 material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 96
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 87
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000011572 manganese Substances 0.000 claims abstract description 81
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 80
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 70
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 15
- 239000012670 alkaline solution Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 11
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 11
- 235000002867 manganese chloride Nutrition 0.000 claims description 11
- 239000011565 manganese chloride Substances 0.000 claims description 11
- 229940099607 manganese chloride Drugs 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052595 hematite Inorganic materials 0.000 description 60
- 239000011019 hematite Substances 0.000 description 60
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 40
- 238000001179 sorption measurement Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 22
- 230000000694 effects Effects 0.000 description 18
- -1 manganese modified hematite Chemical class 0.000 description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000001784 detoxification Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LULLIKNODDLMDQ-UHFFFAOYSA-N arsenic(3+) Chemical compound [As+3] LULLIKNODDLMDQ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The application provides a modified hematite material, which comprises a nano structure formed by a hematite skeleton and a ferro-manganese flocculent aggregate. The preparation method of the modified hematite material comprises the following steps: s1, providing a manganese mixed solution and a ferric iron solution; wherein the manganese mixed solution contains seven-valent manganese and divalent manganese; s2, mixing the manganese mixed solution, the ferric iron solution, the alkaline solution and the bicarbonate solution to obtain a manganese-iron suspension; and S3, performing heating treatment on the manganese-iron suspension to obtain the modified hematite material. The modified hematite material can be used for efficiently treating arsenic-polluted water, in particular arsenic-polluted water containing trivalent arsenic.
Description
Technical Field
The application relates to the field of new materials and water treatment, in particular to a modified hematite material and a preparation method and application thereof.
Background
The improper disposal of mine and industrial arsenic-containing wastewater causes arsenic pollution to become a global environmental problem, and the situation of water environment pollution is particularly serious. The existing arsenic-polluted water treatment technology comprises the following steps: chemical precipitation, flocculation, membrane, ion exchange, adsorption, etc. Compared with other methods, the adsorption method is simple and easy to operate, and the treatment cost can be effectively reduced due to the characteristics of wide source and multiple times of utilization of the adsorbent, so that the adsorption method is a hot spot for researches of a plurality of students. However, the adsorption materials are limited, and the performance of the materials conventionally adopted in the current adsorption method in treating arsenic-polluted water bodies, especially trivalent arsenic-polluted water bodies, still needs to be improved.
In view of the above, it is necessary to provide a modified hematite material, and a preparation method and application thereof, so as to at least solve or alleviate the defect of poor performance of the existing material in treating arsenic-polluted water.
Disclosure of Invention
The application mainly aims to provide a modified hematite material, a preparation method and application thereof, and aims to solve the technical problem that the existing material is poor in performance in the aspect of treating arsenic-polluted water.
In order to achieve the above object, the application provides a modified hematite material, which comprises a nano structure formed by a hematite skeleton and a ferro-manganese flocculent aggregate.
The application also provides a preparation method of the modified hematite material, which comprises the following steps:
s1, providing a manganese mixed solution and a ferric iron solution; wherein the manganese mixed solution contains seven-valent manganese and divalent manganese;
s2, mixing the manganese mixed solution, the ferric iron solution, the alkaline solution and the bicarbonate solution to obtain a manganese-iron suspension;
and S3, performing heating treatment on the manganese-iron suspension to obtain the modified hematite material.
Further, the molar ratio of the heptavalent manganese to the divalent manganese is 2:3-2:4; the molar ratio of the sum of the heptavalent manganese and the divalent manganese to the ferric iron is 0.05:1-0.4:1.
Further, OH in the alkaline solution - With Fe in ferric iron solution 3+ The molar ratio of (2) is 3:1-4:1; HCO in the bicarbonate salt 3 - OH with the alkaline solution - The molar ratio of (2) is 1:5-1:7.
Further, the heptavalent manganese is derived from potassium permanganate; the divalent manganese is derived from one or more of manganese sulfate, manganese chloride and manganese nitrate; the ferric iron solution is derived from one or more of ferric sulfate solution, ferric chloride solution and ferric nitrate solution; the alkaline solution is derived from one or two of potassium hydroxide solution and sodium hydroxide solution; the bicarbonate solution is derived from one or both of a potassium bicarbonate solution and a sodium bicarbonate solution.
Further, the preparation process of the manganese mixed solution comprises the following steps: and mixing the solution of the heptavalent manganese and the solution of the divalent manganese for 2-6 hours to obtain the manganese mixed solution.
Further, the heat treatment includes: and heating the manganese-iron suspension at 70-90 ℃ for 48-72 h.
The application also provides a modified hematite material prepared by the preparation method according to any one of the above.
The application also provides an application of the modified hematite material in treating arsenic-polluted water.
Further, the arsenic-polluted water body contains trivalent arsenic.
Compared with the prior art, the application has at least the following advantages:
1. according to the application, the hematite is successfully modified by introducing the manganese element, so that on one hand, the specific surface area of the hematite is increased, and more reaction sites are provided for removing arsenic in the water environment; on the other hand, the introduction of manganese element obviously improves the oxidation capability of the hematite to trivalent arsenic, and further enhances the oxidation detoxification capability of the hematite to trivalent arsenic. In addition, the hematite is the most stable structure of the iron oxide in the thermomechanics, has good stability, and improves the stability of the material to a certain extent.
2. The application successfully introduces the iron-manganese flocculent aggregate into the hematite skeleton by utilizing an in-situ synthesis-ore phase transformation method, increases the specific surface area of the hematite, and remarkably improves the oxidation adsorption effect of the hematite on trivalent arsenic in water environment. For example, the specific surface area of unmodified hematite is only 44 m 2 The specific surface area of the manganese modified hematite per gram can be increased to 197 and 197 m 2 The specific surface area of the modified hematite is more than 4 times of that of the unmodified hematite; the adsorption amount of the unmodified hematite to arsenic in the water environment is 30 mg/g, and the adsorption amount of the manganese modified hematite to arsenic can be increased to 79 mg/g. Furthermore, manganeseThe removal rate of the modified hematite is increased by about 38-74% compared with the total arsenic removal rate of the hematite, which indicates that the introduction of manganese element obviously enhances the arsenic removal capability of the hematite. In addition, the manganese modified hematite has high arsenic removal capability in a larger pH (3-11) range, and the manganese modified hematite material has more stable total arsenic removal capability in a pH 3-8 range.
3. The material of the application has simple and easy control of the preparation process, convenient operation and stronger oxidation capability to As (III). Compared with Hm, the removal capacity of the manganese modified hematite on As (III) can be increased by about 83% at most, and the removal rate of As (III) is hardly affected by pH in the pH range of 3-11, which shows that the introduction of manganese element obviously enhances the oxidation capacity of the hematite on As (III). The manganese mixed solution provides divalent manganese ions while providing high-valence manganese oxide, and interaction among the divalent manganese ions, the manganese oxide and the iron oxide is realized in the manganese-iron suspension reaction process, so that the manganese modified hematite material is obtained, and the iron doped manganese oxide is also obtained, so that the electron transfer performance of the manganese oxide is improved, and oxidation of As (III) is promoted. For example, the removal rate of As (III) by the modified hematite material may be increased up to about 42% compared to manganese oxide.
In addition, through XPS detection of the material reacted with As (III), after the Hm adsorbs arsenic, the ratio of As (III) to As (V) adsorbed on the surface is 1:0.28, and the As (III) in the manganese modified hematite can reach 1:1.89, further explaining that the manganese modified hematite can not only increase the adsorption quantity of arsenic, but also oxidize the As (III) with high toxicity into the As (V) with low toxicity, thereby reducing the environmental risk of arsenic.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern (XRD) of hematite of comparative example 1-1 and 4 modified hematites of example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of hematite in comparative example 1-1 and Hm-Mn-20% in example 1; wherein a is a transmission electron microscope image of hematite in comparative example 1-1; b is a transmission electron microscope image of Hm-Mn-20% in example 1;
FIG. 3 is a mapping graph of hematite in comparative example 1-1 and Hm-Mn-20% transmission electron microscope in example 1; wherein a is a mapping graph of the hematite transmission electron microscope in comparative example 1-1; b is a mapping graph of the Hm-Mn-20% transmission electron microscope in example 1;
FIG. 4 is a graph of the arsenic removal effect of hematite, 4 modified hematite materials and manganese oxide at different pH conditions; wherein a is an effect diagram of removing arsenic (III) from hematite and 4 modified hematite materials; b is an effect diagram of removing total arsenic from hematite and 4 modified hematite materials; c is an effect diagram of removing arsenic (III) and total arsenic from manganese oxide;
FIG. 5 is a graph showing the effect of hematite and Hm-Mn-20% removal of total arsenic at various initial As (III) concentrations; wherein a is an effect diagram of removing total arsenic from hematite; b is an effect diagram of removing total arsenic by Hm-Mn-20%;
FIG. 6 is a graph showing the effect of hematite and Hm-Mn-20% removal of total arsenic for different reaction durations; wherein a is an effect diagram of removing total arsenic from hematite; b is an effect diagram of removing total arsenic by Hm-Mn-20%;
FIG. 7 is an X-ray photoelectron spectrum (XPS) of hematite and Hm-Mn-20% arsenic adsorption; wherein a is an X-ray photoelectron spectrogram of hematite after arsenic is adsorbed; b is an X-ray photoelectron spectrum of Hm-Mn-20% after arsenic adsorption.
The achievement, functional features and advantages of the present application will be further described with reference to the drawings in connection with the embodiments.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application.
It should be noted that all directional indicators (such as upper and lower … …) in the embodiments of the present application are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicator is changed accordingly.
Moreover, the technical solutions of the embodiments of the present application may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the embodiments, and when the technical solutions are contradictory or cannot be implemented, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection claimed by the present application.
In addition, it should be understood by those skilled in the art that in fig. 4-6 of the drawings of the present specification, the solid portions (e.g., horizontal and vertical lines) within the marked coincidences represent only error bars, and do not affect the understanding of the marked coincidences and the technical effects of the present application.
It should be appreciated that iron oxide has a stronger binding capacity for arsenic than aluminum oxide and manganese oxide, and is more economical than rare earth oxide and zirconium oxide, making it the most commonly used adsorbent in the remediation of arsenic-contaminated water.
Hematite is the most thermodynamically stable structure of iron oxide and has good stability. Although hematite has both stability and excellent properties of iron oxide; however, in water environment, arsenic mainly exists in the form of trivalent arsenic and pentavalent arsenic, the toxicity of As (III) is about 60 times that of As (V), and the adsorption capacity of iron oxide to As (III) is far less than that of As (V), so that the treatment effect of hematite on arsenic-polluted water is poor; moreover, the specific surface area of the hematite is small, and the hematite has a close-packed hexagonal structure, so that the specific surface area of the hematite is difficult to be greatly improved, and the arsenic treatment effect of the hematite is further limited.
Although a technology of oxidizing and then adsorbing is disclosed in the prior art, oxidizing As (III) in a water body into As (V) by using an oxidizing agent such As liquid chlorine, chlorine dioxide and the like, and then adding an adsorbent. The two-step method is inconvenient to operate, low in efficiency, and capable of generating harmful gas to cause secondary pollution and personnel injury, so that further popularization and application of the method are limited. Therefore, the oxidation adsorption method in the prior art is not preferable.
Therefore, the application develops a modified hematite material which is environment-friendly and has the high-efficiency oxidation and detoxification effect on the pollution problem of trivalent arsenic in water environment by modifying with manganese based on hematite.
Through a great deal of research, the application provides a modified hematite material, namely a manganese modified hematite material. The modified hematite material comprises a nano structure formed by a hematite skeleton and a ferro-manganese flocculent aggregate together; specifically, the ferro-manganese flocculent agglomerates are wrapped on the hematite skeleton to form a nano structure together.
The modified hematite material introduces the stability of hematite, has higher specific surface area, and has iron-doped manganese oxide in the iron-manganese flocculent aggregate, so that the electron transfer performance of the manganese oxide can be improved, and the oxidation of As (III) is promoted.
The modified hematite material not only can reduce the total arsenic concentration in the water body, but also can improve the removal efficiency of the hematite on trivalent arsenic in the water body. And compared with hematite, the specific surface area of the modified hematite material is remarkably improved, so that the arsenic treatment efficiency of the modified hematite material can be further improved.
In order to obtain the modified hematite material, the application also provides a preparation method of the modified hematite material, which comprises the following steps:
s1, providing a manganese mixed solution and a ferric iron solution; wherein the manganese mixed solution contains heptavalent manganese and divalent manganese.
Specifically, in the manganese mixed solution, the molar ratio of the heptavalent manganese to the divalent manganese may be 2:3-2:4 (i.e., 2 (3-4)), and may specifically be 2:3. By employing the heptavalent manganese and the divalent manganese, high-valent manganese oxides (tetravalent or/and trivalent) and divalent manganese ions can be provided.
The heptavalent manganese exists in a permanganate, and the heptavalent manganese can be derived from potassium permanganate; the divalent manganese can be derived from one or more of manganese sulfate, manganese chloride and manganese nitrate; the ferric iron solution may be derived from one or more of ferric sulfate solution, ferric chloride solution and ferric nitrate solution.
The preparation process of the manganese mixed solution can comprise the following steps: and mixing the solution of the heptavalent manganese and the solution of the divalent manganese for 2-6 hours to obtain the manganese mixed solution. The manganese mixed solution can be fully reacted by mixing for 2-6 hours.
S2, mixing the manganese mixed solution, the ferric iron solution, the alkaline solution and the bicarbonate solution to obtain a manganese-iron suspension.
Specifically, the manganese mixed solution and the ferric iron solution can be stirred uniformly, then stirring is continuously performed, and the alkaline solution and the bicarbonate solution are added in sequence and mixed uniformly.
By mixing the above 4 reagents, a manganese-iron suspension can be precipitated.
It should be understood that in the step S2, according to the adding ratio of the reactants, the molar ratio of the sum of the heptavalent manganese and the divalent manganese to the ferric iron may be 0.05:1-0.4:1 (i.e., 0.05-0.4:1), i.e., the molar ratio of manganese to ferric iron may be 0.05:1-0.4:1. OH in the alkaline solution - And Fe in the ferric iron solution 3+ The molar ratio of (3) to (4) is 3:1 to (4): 1). HCO in the bicarbonate salt 3 - OH with the alkaline solution - The molar ratio of (2) is 1:5-1:7 (i.e., 1 (5-7)).
It is noted that by using the alkaline solution, amorphous iron oxide can be precipitated; by using the bicarbonate, the suspension can be placed in an alkaline buffer system.
The alkaline solution is derived from one or two of potassium hydroxide solution and sodium hydroxide solution; the bicarbonate solution is derived from one or both of potassium bicarbonate and sodium bicarbonate solution.
And S3, performing heating treatment on the manganese-iron suspension to obtain the modified hematite material.
The heat treatment includes: and heating the manganese-iron suspension at 70-90 ℃ for 48-72 h. By performing the heating treatment, amorphous iron oxide can be converted into hematite; the manganese-iron suspension may be sealed during the heat treatment.
Further, after the heating treatment, the product obtained by the heating treatment may be washed and freeze-dried in sequence to obtain the modified hematite material.
The modified hematite material prepared by the embodiment can be used for oxidizing and adsorbing trivalent arsenic in polluted water, and can be used for directly adsorbing pentavalent arsenic. The modified hematite material forms a ferro-manganese flocculent aggregate on a hematite (Hm) framework, wherein the manganese modified hematite not only can increase the specific surface area of the hematite, but also introduces manganese element, and provides a certain foundation for oxidation detoxification and adsorption fixation of trivalent arsenic ions in a subsequent water environment.
According to the manganese-modified hematite, on one hand, the specific surface area of the hematite is increased, and the problem of low adsorption capacity of the hematite is solved to a certain extent; on the other hand, the oxidation capability of the hematite on trivalent arsenic is obviously improved, and the problem of poor detoxification effect of the hematite on the trivalent arsenic is solved.
Based on the preparation method, the application also provides a modified hematite material, which is prepared by adopting the preparation method according to any embodiment.
Based on the modified hematite material, the application also provides an application of the modified hematite material in treating arsenic-polluted water. The pH of the arsenic-polluted water body can be 3-11, and further can be 3-8; the preferable treatment time length can be 6-24 hours.
Further, the arsenic-polluted water body can contain trivalent arsenic, and the concentration of the trivalent arsenic can be 10-500 mg/L. That is, the modified hematite material can oxidize and adsorb trivalent arsenic to realize efficient purification of arsenic-polluted water with trivalent arsenic. In addition, the arsenic in the arsenic-contaminated water body may be trivalent arsenic only; or mostly trivalent arsenic; it may contain both trivalent arsenic and pentavalent arsenic.
For the purpose of facilitating a specific understanding of the application by those skilled in the art, reference will now be made to the accompanying examples:
note that: in each of the following examples and comparative examples, as (iii) in the As (iii) solution is provided by sodium arsenite.
Example 1
The embodiment is the preparation of modified hematite materials with different ferromanganese ratios.
1. The preparation of the modified hematite material with the ferromanganese molar ratio of 0.05:1 comprises the following steps:
(1) 10 mL of 0.02 mol/L potassium permanganate solution and 10 mL of 0.03 mol/L manganese chloride solution are mixed, and the mixture is stirred at a speed of 200 r/min for 4 h to obtain a manganese mixed solution for later use.
(2) Adding the manganese mixed solution obtained in the step (1) into 50 mL of 0.2 mol/L ferric nitrate solution, uniformly stirring, adding 30 mL of 1 mol/L potassium hydroxide solution and 5 mL of 1 mol/L sodium bicarbonate solution, and uniformly stirring to obtain manganese-iron suspension;
(3) And (3) sealing the manganese-iron suspension obtained in the step (2), heating at 90 ℃ for 60 h, separating out the obtained solid product, washing the solid product with pure water for 3 times, and freeze-drying at-55 ℃ for 12 h to obtain the modified hematite material.
The molar ratio of ferromanganese of the obtained modified hematite material is 0.05:1, namely the molar percentage of ferromanganese is 5 percent, and the obtained modified hematite material is recorded as Hm-Mn-5 percent.
2. Preparation of modified hematite materials with ferromanganese molar ratios of 0.1:1, 0.2:1, 0.4:1:
in comparison with part 1 of this example, only the molar concentrations of potassium permanganate and manganese chloride were changed.
Namely: controlling the molar ratio of potassium permanganate to manganese chloride to be 2:3, respectively adjusting the concentrations of the potassium permanganate and the manganese chloride to 0.04 mol/L of potassium permanganate and 0.06 mol/L of manganese chloride, 0.08 mol/L of potassium permanganate and 0.12 mol/L of manganese chloride, 0.16 mol/L of potassium permanganate and 0.24 mol/L of manganese chloride, and carrying out the rest preparation specific processes according to the steps (1) - (3) in the part 1 of the embodiment to obtain the modified hematite material with the manganese-iron molar ratio of 0.1:1, 0.2:1 and 0.4:1 respectively.
The modified hematite materials with the molar ratios of ferromanganese of 0.1:1, 0.2:1 and 0.4:1 are respectively marked as Hm-Mn-10%, hm-Mn-20% and Hm-Mn-40%.
In this example, 4 manganese-modified hematite materials of different ferromanganese ratios, hm-Mn-5%, hm-Mn-10%, hm-Mn-20% and Hm-Mn-40%, respectively, were finally prepared.
Comparative examples 1-1: preparation of hematite
To 50 mL of a 0.2 mol/L ferric nitrate solution, 30 mL of a 1 mol/L potassium hydroxide solution and 5 mL of a 1 mol/L sodium bicarbonate solution were added, and the mixture was stirred uniformly to obtain an iron suspension. The resulting iron suspension was sealed and then heated at 90℃for 60 h, then the resulting solid product was isolated, washed 3 times with pure water and freeze-dried at-55℃for 12 h to give hematite (Hm).
Comparative examples 1-2: preparation of manganese oxides
100 mL of 0.02 mol/L potassium permanganate solution and 100 mL of 0.03 mol/L manganese chloride solution are mixed, and the mixture is stirred at a speed of 200 r/min for 4 h, so that the obtained manganese mixed solution is ready for use. The obtained manganese-mixed solution is sealed and then heated at 90 ℃ for 60 h, then the obtained solid product is separated, the obtained solid product is washed for 3 times by pure water, and the obtained solid product is freeze-dried at-55 ℃ for 12 h, so as to obtain manganese oxide.
Analytical example 1
Analysis was performed for example 1 and comparative example 1-1:
as can be seen by referring to the XRD pattern in fig. 1, both example 1 and comparative example 1-1 produced a series of hematite-based materials.
As can be seen by referring to the TEM images in fig. 2 (a) and (b), the hematite is a relatively regular rhombohedron, and there are also some small irregular particles, which are likely to be fine hematite nanoparticles.
However, the manganese modified hematite material (Hm-Mn-20%) has many flocs in addition to rhombohedra, and it can be seen that the fine filiform substances are randomly gathered and staggered together. The formation of large numbers of flocculent agglomerates may be responsible for the dramatic increase in specific surface area of the manganese modified hematite, which may provide more sites for arsenic binding.
Referring to FIG. 3 (converted from color chart), iron elements on hematite are uniformly distributed, while iron and manganese on manganese modified hematite material (Hm-Mn-20%) are unevenly distributed, wherein Fe is mainly distributed on more regular particles, i.e. hematite, a small amount of iron is distributed on flocculent clusters, and Mn enrichment is mainly related to flocculent clusters.
Referring to fig. 1-3, and based on the analysis of this analysis example, the manganese-modified hematite material (Hm-Mn-20%) has a nanostructure formed by a hematite skeleton and a ferro-manganese flocculent aggregate, and the ferro-manganese flocculent aggregate is wrapped on the hematite skeleton.
In the present analysis example, the specific surface area of the hematite was only 44 and m as a result of the specific surface area detection of the unmodified hematite and the manganese-modified hematite material (Hm-Mn-20%) 2 The specific surface area of the manganese modified hematite per gram can be increased to 197 and 197 m 2 And/g. The introduction of manganese proves that the specific surface area of the hematite is successfully increased, and the problems of small specific surface area and few binding sites of the hematite are solved to a certain extent.
Example 2
The 4 modified hematite materials of example 1 were added to different groups of As (iii) solutions, respectively (the groups have a one-to-one correspondence with the types of modified hematite). Wherein each group is provided with a plurality of parts of arsenic-containing solution (pH is adjusted by using 0.1M HCl or 0.1M NaOH) according to the pH value of 3-11, the volume of each part of As (III) solution is 5 mL, and the concentration of As (III) is 100 mg/L; the addition amount of the modified hematite material in each part of As (III) solution is 10 mg.
After 24 h of oscillation reaction at room temperature and 60 r/min, sampling, measuring the concentration of As (III) and total arsenic in the solution by using an atomic fluorescence spectrometer, and calculating to obtain the removal rate of Hm-Mn-5%, hm-Mn-10%, hm-Mn-20% and Hm-Mn-40% to As (III) and total arsenic.
Comparative example 2-1
Hm in comparative example 1-1 was added to As (III) solutions of different pH values (pH=3 to 11), respectively; the volume of each part of As (III) solution is 5 mL, the concentration of As (III) is 100 mg/L, and the addition amount of hematite (Hm) in each part of As (III) solution is 10 mg.
After 24 h of oscillation reaction at room temperature and 60 r/min, sampling, measuring the As (III) and total arsenic concentration in the solution by using an atomic fluorescence spectrometer, and calculating to obtain the removal rate of Hm to the As (III) and total arsenic. Wherein the pH value of the As (III) solution is regulated by using 0.1M HCl or NaOH.
Comparative examples 2 to 2
Respectively adding the manganese oxide in comparative examples 1-2 into As (III) solutions with different pH values (pH=3-11); the volume of each part of As (III) solution is 5 mL, the concentration of As (III) is 100 mg/L, and the addition amount of manganese oxide in each part of As (III) solution is 10 mg.
After 24 h of oscillation reaction at room temperature and 60 r/min, sampling, measuring the As (III) and total arsenic concentration in the solution by using an atomic fluorescence spectrometer, and calculating to obtain the removal rate of the manganese oxide to the As (III) and total arsenic. Wherein the pH value of the As (III) solution is regulated by using 0.1M HCl or NaOH.
Analytical example 2
Analysis was performed on example 2, comparative example 2-1, comparative example 2-2:
referring to fig. 4, compared with Hm, the removal capability of total arsenic of the modified hematite material provided in example 1 is improved by about 38-74%; and the modified hematite material has a pH value of 3-8, and the total arsenic removal rate is in a higher and more stable state. Compared with Hm, the removal capacity of the modified hematite on As (III) can be increased by about 83% at most, and in the pH range of 3-11, the removal rate of the modified hematite material on As (III) is hardly affected by pH, which shows that the introduction of manganese element obviously enhances the oxidation capacity and removal capacity of the hematite on As (III). In addition, compared with manganese oxide, the removal capacity of the modified hematite material provided in the embodiment 1 to total arsenic is improved by about 33-77%, and the removal rate of As (III) can be increased by about 42% at the highest, which shows that the presence of iron element also enhances the oxidation capacity of manganese oxide to As (III), and the synergistic enhancement effect between manganese and hematite is reflected.
Specifically, when the pH of the As (III) solution is 3-11, the removal rate of the modified hematite (taking Hm-Mn-20% As an example) to the total arsenic is 52.0-79.6%, the removal rate of the hematite to the total arsenic is 6.9-21.0%, and the removal rate of the manganese oxide to the total arsenic is 2.4-15.5%; the removal rate of the modified hematite (Hm-Mn-20% for example) to As (III) is between 85.1 and 92.2%, the removal rate of the hematite to As (III) is between 5.0 and 17.6%, and the removal rate of the manganese oxide to As (III) is between 49.8 and 66.7%.
In this analysis example, the removal rate of total arsenic and As (III) by the manganese modified hematite is significantly higher than the sum of hematite and manganese oxide, producing unexpected technical effects.
Example 3
The Hm-Mn-20% in example 1 was added to the As (III) solutions of different preset concentrations, the volume of each part of the As (III) solution was 5.5 mL, the addition amount of the Hm-Mn-20% in each part of the As (III) solution was 10 mg, the pH of the As (III) solution was 8, and the concentration of the As (III) solution of the preset concentration was 10 to 500 mg/L.
The reaction temperature is room temperature, after 24 h of oscillation reaction under the condition of 60 r/min, sampling is carried out, the total arsenic concentration in the solution is measured by using an atomic fluorescence spectrometer, and the adsorption quantity of Hm-Mn-20% to the total arsenic is calculated.
Comparative example 3
Hm in comparative example 1-1 was added to the As (III) solutions of different preset concentrations, the volume of each part of the As (III) solution was 5 mL, the addition amount of hematite (Hm) in each part of the As (III) solution was 10 mg, the pH of each part of the As (III) solution was 8, and the concentration of the As (III) solution of the preset concentration was 10-500 mg/L.
The reaction temperature is room temperature, after 24 h of oscillation reaction is carried out under the condition of 60 r/min, sampling is carried out, the total arsenic concentration in the solution is measured by using an atomic fluorescence spectrometer, and the adsorption quantity of Hm to the total arsenic is calculated.
Analytical example 3
Analysis was performed for example 3 and comparative example 3:
as can be seen from FIG. 5, as the initial concentration of As (III) solution increases, the adsorption amounts of Hm-Mn-20% and Hm to total arsenic gradually increaseAdding and then smoothing; the maximum adsorption capacity of Hm to total arsenic is 30 mg/g, and the maximum adsorption capacity of Hm-Mn-20% to total arsenic can be increased to 79 mg/g (FIG. 5 abscissa C e For equilibrium concentration, the equilibrium concentration is positively correlated with the initial concentration).
Example 4
Hm-Mn-20% in example 1 was added to the As (III) solutions each having a volume of 5 mL, a concentration of 100 mg/L, and a pH of 8, respectively, in an amount of 10 mg/part of Hm-Mn-20%.
The reaction temperature is room temperature, the oscillation reaction is carried out for 2-1440 min under the condition of 60 r/min, for example, the reaction time is 2 min, 5 min, 10 min, 20 min, 40 min and the like, sampling is carried out, the total arsenic concentration in the solution is measured by using an atomic fluorescence spectrometer, and the adsorption quantity of Hm-Mn-20% on the total arsenic and the removal rate of As (III) are calculated.
In addition, after the material reacted for 1440 min is washed, the material is dried to be detected, and XPS is utilized to detect the valence state and the content of arsenic adsorbed by Hm-Mn-20% material after the reaction.
Comparative example 4
Hm in comparative example 1-1 was added to the As (III) solutions each having a volume of 5 mL, a concentration of 100 mg/L of As (III), an addition amount of hematite (Hm) in each of the As (III) solutions was 10 mg, and a pH of the As (III) solution was 8, respectively.
The reaction temperature is room temperature, the oscillation reaction is carried out for 2-1440 min under the condition of 60 r/min, for example, the reaction time is 2 min, 5 min, 10 min, 20 min, 40 min and the like, sampling is carried out, the total arsenic concentration in the solution is measured by using an atomic fluorescence spectrometer, and the adsorption capacity of Hm to the total arsenic and the removal rate of As (III) are calculated.
In addition, after the material reacted for 1440 min is washed, the material is dried to be detected, and the valence state and the content of arsenic adsorbed by the Hm material after the reaction are detected by XPS.
Analytical example 4
Analysis was performed for example 4 and comparative example 4:
referring to FIG. 6, after 240 min the Hm is balanced for total arsenic removal, while Hm-Mn-20% is balanced after 360 min, and the Hm-Mn-20% adsorption equilibrium time is slower, possibly related to trivalent arsenic oxidation. Although the adsorption equilibrium time is slightly slower, after the adsorption equilibrium, the adsorption quantity of Hm to total arsenic is only 6.05 mg/g, and the adsorption quantity of Hm-Mn-20% to total arsenic can reach 23.91 mg/g.
In addition, according to measurement and calculation, the removal rate of the solution As (III) is only 14.2% for Hm and 84% for Hm-Mn-20% at 360 min, which indicates that the manganese modified hematite can effectively oxidize and remove As (III) in water environment.
Referring to FIG. 7, after Hm-Mn-20% and Hm react with As (III) for 1440 min, in an As 3d fine spectrum of an XPS chart of the material, after Hm adsorbs arsenic, the ratio of As (III) to As (V) adsorbed on the surface is 1:0.28, and the As (III): as (V) in Hm-Mn-20% can reach 1:1.89, which indicates that Hm-Mn-20% has stronger oxidizing capability on As (III).
In the above technical solution of the present application, the above is only a preferred embodiment of the present application, and therefore, the patent scope of the present application is not limited thereto, and all the equivalent structural changes made by the description of the present application and the content of the accompanying drawings or the direct/indirect application in other related technical fields are included in the patent protection scope of the present application.
Claims (5)
1. The preparation method of the modified hematite material is characterized by comprising the following steps:
s1, providing a manganese mixed solution and a ferric iron solution; wherein the manganese mixed solution contains seven-valent manganese and divalent manganese;
the molar ratio of the heptavalent manganese to the divalent manganese is 2:3-2:4; the molar ratio of the sum of the heptavalent manganese and the divalent manganese to the ferric iron is 0.05:1-0.4:1;
the heptavalent manganese is derived from potassium permanganate; the divalent manganese is derived from one or more of manganese sulfate, manganese chloride and manganese nitrate; the ferric iron solution is derived from one or more of ferric sulfate solution, ferric chloride solution and ferric nitrate solution;
s2, mixing the manganese mixed solution, the ferric iron solution, the alkaline solution and the bicarbonate solution to obtain a manganese-iron suspension;
OH in the alkaline solution - And Fe in the ferric iron solution 3+ The molar ratio of (2) is 3:1-4:1; HCO in the bicarbonate salt 3 - OH with the alkaline solution - The molar ratio of (2) is 1:5-1:7;
the alkaline solution is derived from one or two of potassium hydroxide solution and sodium hydroxide solution; the bicarbonate solution is derived from one or both of potassium bicarbonate solution and sodium bicarbonate solution;
s3, carrying out heating treatment on the manganese-iron suspension to obtain a modified hematite material; the modified hematite material comprises a nano structure formed by a hematite skeleton and a ferro-manganese flocculent aggregate together;
the heat treatment includes: and heating the manganese-iron suspension at 70-90 ℃ for 48-72 h.
2. The preparation method according to claim 1, wherein the preparation process of the manganese mixed solution comprises: and mixing the solution of the heptavalent manganese and the solution of the divalent manganese for 2-6 hours to obtain the manganese mixed solution.
3. A modified hematite material characterized by being prepared by the preparation method according to claim 1 or 2.
4. Use of the modified hematite material of claim 3 for the treatment of arsenic-contaminated water.
5. The use of claim 4, wherein the arsenic-contaminated water body comprises trivalent arsenic.
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