CN117358193A - Use of iodine scavenger, fluorine scavenger and ferro-manganese composite metal oxide - Google Patents
Use of iodine scavenger, fluorine scavenger and ferro-manganese composite metal oxide Download PDFInfo
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- CN117358193A CN117358193A CN202311386163.3A CN202311386163A CN117358193A CN 117358193 A CN117358193 A CN 117358193A CN 202311386163 A CN202311386163 A CN 202311386163A CN 117358193 A CN117358193 A CN 117358193A
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- 239000002131 composite material Substances 0.000 title claims abstract description 130
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 130
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 130
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 126
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011630 iodine Substances 0.000 title claims abstract description 76
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 76
- 239000011737 fluorine Substances 0.000 title claims abstract description 52
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 52
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims description 51
- 239000002516 radical scavenger Substances 0.000 title claims description 28
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 95
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 43
- 230000000694 effects Effects 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 39
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 36
- 239000011572 manganese Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 13
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000701 coagulant Substances 0.000 claims description 3
- 229940006461 iodide ion Drugs 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 9
- 150000004694 iodide salts Chemical class 0.000 abstract description 9
- 239000011218 binary composite Substances 0.000 abstract description 2
- 235000013980 iron oxide Nutrition 0.000 description 33
- 239000000243 solution Substances 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 12
- 238000011069 regeneration method Methods 0.000 description 12
- -1 iodide ions Chemical class 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012528 membrane Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 239000003673 groundwater Substances 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000012286 potassium permanganate Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- GEOVEUCEIQCBKH-UHFFFAOYSA-N hypoiodous acid Chemical compound IO GEOVEUCEIQCBKH-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000012692 Fe precursor Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 208000024799 Thyroid disease Diseases 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- AAUNBWYUJICUKP-UHFFFAOYSA-N hypoiodite Chemical compound I[O-] AAUNBWYUJICUKP-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 229940005633 iodate ion Drugs 0.000 description 1
- PDJAZCSYYQODQF-UHFFFAOYSA-N iodine monofluoride Chemical compound IF PDJAZCSYYQODQF-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 229960001841 potassium permanganate Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The iodine removing agent comprises an iron-manganese composite metal oxide, wherein the iron-manganese composite metal oxide is a composite metal oxide of iron oxide and manganese oxide. The binary composite metal oxide can be used as an iodine remover and a fluorine remover to effectively remove iodides and fluorides in iodine-containing and fluorine-containing water.
Description
Technical Field
The embodiments of the present application relate to the field of water treatment, and in particular, but not limited to, use of iodine scavenger, fluorine scavenger and iron-manganese composite metal oxide.
Background
In areas where there is a lot of groundwater with high iodine (e.g., total iodine content >100 μg/L), the population affected by excessive iodine in water source is large, which is liable to cause thyroid diseases. At present, the mature iodine removal technology is limited in the fields of nuclear wastewater and industrial wastewater, including a chemical precipitation method, a membrane separation method, a biological method, an adsorption method and the like. Because of the safety specificity of the drinking water, the adsorption method is more suitable for large-scale engineering application due to the advantages of small dosage of chemical agents, simple and convenient operation and the like.
In periodate groundwater, iodine exists mainly in the form of iodide, and other inorganic anions such as fluoride coexist with iodine. The exceeding of the concentration of the iodide is mostly accompanied by the exceeding of the fluoride. In addition, when groundwater is treated by a pre-oxidation technique, iodide ions are easily oxidized into elemental iodine or iodate ions. However, general adsorbents cannot simultaneously and efficiently remove iodine in various forms. Therefore, constructing a material which can efficiently remove iodine in various forms and fluoride is a difficult problem in the current water treatment field.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the application.
The embodiment of the application provides an iodine remover, a fluorine remover and application of an iron-manganese composite metal oxide, wherein the iodine remover and the fluorine remover can effectively remove iodides and fluorides in iodine-containing and fluorine-containing water.
The embodiment of the application provides an iodine remover, which comprises an iron-manganese composite metal oxide, wherein the iron-manganese composite metal oxide is a composite metal oxide of manganese oxide and iron oxide.
In an exemplary embodiment of the iodine scavenger of the present application, in the iron-manganese composite metal oxide, a molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1 (0.1 to 10).
In exemplary embodiments of the iodine scavenger of the present application, the manganese oxide and the iron oxide in the iron-manganese composite metal oxide may each be amorphous.
In exemplary embodiments of the iodine scavenger of the present application, the manganese oxide may include MnO 2 The iron oxide may include Fe 3 O 4 。
The embodiment of the application provides a fluorine removing agent, which comprises a ferro-manganese composite metal oxide, wherein the ferro-manganese composite metal oxide is a composite metal oxide of manganese oxide and ferric oxide.
In an exemplary embodiment of the fluorine scavenger of the present application, in the ferro-manganese composite metal oxide, a molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1 (0.1 to 10).
In exemplary embodiments of the fluorine scavenger of the present application, the manganese oxide and the iron oxide in the iron-manganese composite metal oxide may each be amorphous.
In exemplary embodiments of the fluorine scavenger of the present application, the manganese oxide may include MnO 2 The iron oxide may include Fe 3 O 4 。
The embodiment of the application also provides an application of the ferro-manganese composite metal oxide, which comprises the steps of adopting the ferro-manganese composite metal oxide to remove iodine in water, or remove fluorine in water, or remove iodine and fluorine in water; the ferro-manganese composite metal oxide is a composite metal oxide of manganese oxide and ferric oxide.
In an exemplary embodiment of the use of the iron-manganese composite metal oxide of the present application, in the iron-manganese composite metal oxide, a molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1 (0.1 to 10).
In exemplary embodiments of the use of the iron-manganese composite metal oxide of the present application, both the manganese oxide and the iron oxide in the iron-manganese composite metal oxide may be amorphous.
In exemplary embodiments of use of the iron-manganese composite metal oxides of the present application, the manganese oxide may include MnO 2 The iron oxide may include Fe 3 O 4 。
In an exemplary embodiment of the present application, the use of the ferro-manganese composite metal oxide includes:
adding the iron-manganese composite metal oxide into water to be treated containing any one or two of iodine and fluorine, stirring until the treated water meets at least one of the following conditions, and performing solid-liquid separation:
a) The iodide concentration is less than or equal to 100 mug/L;
b) The concentration of fluoride is less than or equal to 1mg/L.
In exemplary embodiments of the present application, the use of the ferro-manganese composite metal oxide may further include either or both of the following operations:
c) When the iodine removal effect does not reach the expected value, regulating the pH value of the iron-manganese composite metal oxide to regenerate the iron-manganese composite metal oxide;
d) And when the fluorine removal effect does not reach the expected value, regenerating the ferro-manganese composite metal oxide by adopting a method of adding an aluminum-containing coagulant into the system.
In an exemplary embodiment of the present application, the amount of the iron-manganese composite metal oxide added to 1L of the water to be treated may be 0.5g to 1.5g.
In an exemplary embodiment of the present application, the initial iodide ion concentration in the water to be treated may be not higher than 300 μg/L, and/or the initial fluoride ion concentration may be not higher than 4mg/L.
The iodine scavenger and the fluorine scavenger of the embodiment of the application can obtain the following effects:
(1) The method has good removal effect on iodine and fluorine in water (such as groundwater), can remove iodide or fluoride in water independently, and can remove iodide and fluoride in water simultaneously and efficiently; in addition, the metal elements in the iron-manganese composite metal oxide are nontoxic and are suitable for treating drinking water;
(2) The method has a morphological regulation effect on iodide ions, can improve the adsorption and oxidation effects of the iodide ions, and has a higher adsorption effect on iodine simple substances and iodate radicals;
(3) The preparation methods of the ferro-manganese composite metal oxide, the iodine remover and the fluorine remover are simple, and the preparation cost is low;
(4) The regeneration and separation method of the ferro-manganese composite metal oxide is simple and convenient, and can be repeatedly used, so that the cost of iodine removal and fluorine removal is reduced, and the ferro-manganese composite metal oxide is suitable for large-scale application.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. Other advantages of the present application may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The accompanying drawings are included to provide an understanding of the technical aspects of the present application, and are incorporated in and constitute a part of this specification, illustrate the technical aspects of the present application and together with the examples of the present application, and not constitute a limitation of the technical aspects of the present application.
FIG. 1A shows MnO in the form of commercially available gamma crystals of a ferro-manganese composite metal oxide FMO prepared in example 1 of the present application 2 X-ray polycrystalline diffraction patterns of commercial ferroferric oxide type Fe oxides;
FIG. 1B is an X-ray photoelectron spectroscopy fine map of the ferro-manganese element in FMO;
FIG. 1C is an X-ray photoelectron spectroscopy fine map of manganese element in FMO;
FIG. 2 shows the effect of removing iodide and fluoride simultaneously with FMO (1:0.5) of the iron-manganese composite metal oxide prepared in example 1 of the present application;
FIG. 3 shows the iodide removal effect of the iron-manganese composite metal oxide FMO prepared in example 1 of the present application at different molar ratios when iodine is removed alone;
FIG. 4 shows fluoride removal effect of the iron-manganese composite metal oxide FMO prepared in example 1 of the present application at different molar ratios when fluorine is removed alone;
FIG. 5 shows the concentration change of iodine form when the iron-manganese composite metal oxide FMO (1:0.5) prepared in example 1 of the present application is used to remove iodide from water;
FIG. 6 is a XPS high resolution spectrum of the iron-manganese composite metal oxide FMO (1:0.5) prepared in example 1 of the present application after iodide removal from water;
FIG. 7 shows MnO of iron-manganese composite metal oxide FMO (1:0.5), commercially available ferroferric oxide, and commercially available gamma crystal form prepared in example 1 of the present application 2 Is effective in removing iodide or fluoride;
FIG. 8 shows MnO of iron-manganese composite metal oxide FMO (1:0.5), commercially available ferroferric oxide, and commercially available gamma crystal form prepared in example 1 of the present application 2 Is effective in removing iodide or fluoride;
FIG. 9 shows the effect of removing iodides or fluorides of the iron-manganese composite metal oxide FMO (1:0.5) prepared in example 1 of the present application after regeneration with regeneration solutions of different pH values.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be arbitrarily combined with each other.
The embodiment of the application provides an iodine scavenger, which comprises a ferro-manganese composite metal oxide (named as FMO in the application), wherein the ferro-manganese composite metal oxide is a composite metal oxide of manganese oxide and iron oxide.
In an exemplary embodiment of the iodine scavenger of the present application, in the iron-manganese composite metal oxide, a molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1 (0.1 to 10). For example, the molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or 1:10.
In exemplary embodiments of the iodine scavenger of the present application, the manganese oxide and the iron oxide in the iron-manganese composite metal oxide may each be amorphous.
In exemplary embodiments of the iodine scavenger of the present application, the manganese oxide may include MnO 2 The iron oxide may include Fe 3 O 4 。
In exemplary embodiments of the iodine scavenger of the present application, the manganese oxide may be MnO 2 The iron oxide may be Fe 3 O 4 。
The embodiment of the application provides a fluorine removing agent, which comprises a ferro-manganese composite metal oxide, wherein the ferro-manganese composite metal oxide is a composite metal oxide of manganese oxide and ferric oxide.
In an exemplary embodiment of the fluorine scavenger of the present application, in the ferro-manganese composite metal oxide, a molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1 (0.1 to 10). For example, the molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or 1:10.
In exemplary embodiments of the fluorine scavenger of the present application, the manganese oxide and the iron oxide in the iron-manganese composite metal oxide may each be amorphous.
In exemplary embodiments of the fluorine scavenger of the present application, the manganese oxide may include MnO 2 The iron oxide may include Fe 3 O 4 。
In exemplary embodiments of the fluorine scavenger of the present application, the manganese oxide may be MnO 2 The iron oxide may be Fe 3 O 4 。
The embodiment of the application also provides an application of the ferro-manganese composite metal oxide, which comprises the steps of adopting the ferro-manganese composite metal oxide to remove iodine in water, or remove fluorine in water, or remove iodine and fluorine in water; the ferro-manganese composite metal oxide is a composite metal oxide of manganese oxide and ferric oxide.
In an exemplary embodiment of the use of the iron-manganese composite metal oxide of the present application, in the iron-manganese composite metal oxide, a molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1 (0.1 to 10). For example, the molar ratio of Mn in the manganese oxide to Fe in the iron oxide may be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or 1:10.
In exemplary embodiments of the use of the iron-manganese composite metal oxide of the present application, both the manganese oxide and the iron oxide in the iron-manganese composite metal oxide may be amorphous.
In exemplary embodiments of use of the iron-manganese composite metal oxides of the present application, the manganese oxide may include MnO 2 The iron oxide may include Fe 3 O 4 。
In exemplary embodiments of use of the iron-manganese composite metal oxide of the present application, the manganese oxide may be MnO 2 The iron oxide may be Fe 3 O 4 。
In an exemplary embodiment of the present application, the use of the ferro-manganese composite metal oxide includes:
adding the iron-manganese composite metal oxide into water to be treated containing any one or two of iodine and fluorine, stirring until the treated water meets at least one of the following conditions, and performing solid-liquid separation:
a) The iodide concentration is less than or equal to 100 mug/L;
b) The concentration of fluoride is less than or equal to 1mg/L.
In an exemplary embodiment of the present application, the use of the ferro-manganese composite metal oxide includes: adding the iron-manganese composite metal oxide into water to be treated containing iodine, stirring until the treated water meets the iodide concentration of less than 100 mug/L, and carrying out solid-liquid separation.
In an exemplary embodiment of the present application, the use of the ferro-manganese composite metal oxide includes: adding the ferro-manganese composite metal oxide into the water to be treated containing fluorine, stirring until the concentration of the fluoride in the treated water is less than 1mg/L, and carrying out solid-liquid separation.
In an exemplary embodiment of the present application, the use of the ferro-manganese composite metal oxide includes: adding the ferro-manganese composite metal oxide into water to be treated containing iodine and fluorine, stirring until the treated water meets at least one of the following conditions, and carrying out solid-liquid separation:
a) The iodide concentration is less than or equal to 100 mug/L;
b) The concentration of fluoride is less than or equal to 1mg/L.
In exemplary embodiments of the use of the iron-manganese composite metal oxide of the present application, the use may further include either or both of the following operations:
c) When the iodine removal effect is not expected, for example, the iodide concentration in the treated water is not more than 100 mug/L, and the pH value of the ferromanganese composite metal oxide is adjusted to regenerate the ferromanganese composite metal oxide;
d) When the fluorine removal effect is not desired, for example, the fluoride concentration in the treated water is not more than 1mg/L, and the ferro-manganese composite metal oxide is regenerated by adding an aluminum-containing coagulant into the system.
In an exemplary embodiment of the use of the iron-manganese composite metal oxide of the present application, the amount of the iron-manganese composite metal oxide added to 1L of the water to be treated may be 0.5g to 1.5g, for example, may be 0.5g, 1g, or 1.5g.
In an exemplary embodiment of the present application, the initial iodide ion concentration in the water to be treated may be not higher than 300 μg/L.
In an exemplary embodiment of the present application, the initial fluoride ion concentration in the water to be treated may be not higher than 4mg/L.
In exemplary embodiments of use of the iron-manganese composite metal oxides of the present application, the solid-liquid separation methods include precipitation, membrane filtration, centrifugation, air flotation, sand filtration, and the like.
In an exemplary embodiment of the use of the iron-manganese composite metal oxide of the present application, the adjusting the pH of the iron-manganese composite metal oxide comprises: the pH of the iron-manganese composite metal oxide after the adsorption of iodide (which may also include the adsorption of fluoride) is adjusted to 9 to 11.
For example, 1g of the ferromanganese composite metal oxide saturated with the adsorbed iodide may be thoroughly mixed with 1L of the alkali-containing water;
wherein the pH value of the alkaline water is 9 to 11.
In an exemplary embodiment of the application of the ferro-manganese composite metal oxide of the present application, the regeneration may be performed in a regeneration device with a stirrer, the volume of the regeneration device may be 1L, the stirring speed may be 500r/min, and the stirring and mixing may be performed for 24 hours.
In an exemplary embodiment of the use of the iron-manganese composite metal oxide of the present application, the stirring may be performed by a magnetic stirrer, the rotation speed may be 400rpm to 600rpm, for example, 500rpm, and the stirring time may be 2 hours to 4 hours, for example, may be 2 hours.
In an exemplary embodiment of the present application, the ferro-manganese composite metal oxide may be obtained by the following preparation method:
mixing a manganese precursor compound and an iron precursor compound in proportion to obtain a mixed solution; and (3) carrying out solid-liquid separation and drying on the mixed solution to obtain the FMO binary metal composite oxide.
In the method for preparing the ferro-manganese composite oxide provided in the embodiment of the present application, the precursor compound of manganese may be any one or more of potassium permanganate, manganese sulfate, and manganese chloride, and the precursor compound of iron may be any one or more of ferrous sulfate (e.g., ferrous sulfate heptahydrate), ferrous nitrate, and ferrous chloride; the manganese precursor compound and the iron precursor compound may be in the form of aqueous solutions, and their solution concentrations may be the same, and may be mixed in proportion.
In the method for preparing the iron-manganese composite oxide provided in the embodiment of the present application, the stirring and mixing manner may be performed by a magnetic stirrer, the rotation speed may be 400r/min to 600r/min, for example, 500r/min, and the stirring time may be 2 hours to 4 hours, for example, may be 2 hours, 3 hours or 4 hours.
In the preparation method of the iron-manganese composite oxide provided by the embodiment of the application, the solid-liquid separation of the mixed solution can be realized through the modes of standing precipitation, centrifugation, membrane separation and the like, for example, the solid-liquid separation is realized through filtration by a filter membrane, and the pore diameter of the filter membrane can be 0.45 micrometer.
In the preparation method of the ferro-manganese composite oxide provided by the embodiment of the application, the drying can be performed through freeze drying, the freezing temperature can be between-80 ℃ and-50 ℃, and the drying time can be between 5 hours and 8 hours.
Example 1: preparation of iron-manganese composite metal oxide FMO
2.78g FeSO was taken 4 ·7H 2 O and 1.58g KMnO 4 Respectively dissolving in 1L of water to obtain ferrous sulfate solution and potassium permanganate solution with the concentration of 0.01 mol/L. 500mL of ferrous sulfate solution and 500mL of potassium permanganate solution are respectively taken and mixed and then stirred for 2h under the magnetic stirring condition. Filtering the mixed solution of ferrous sulfate solution and potassium permanganate solution through a filter membrane with the pore diameter of 0.45 micrometers; and then placing the filter membrane in a refrigerator at the temperature of minus 80 ℃ for quick freezing for 20min, taking out, placing the filter membrane in a freeze dryer for drying for 5h, scraping and grinding the dried powder on the membrane to obtain FMO binary composite metal oxide powder, wherein the molar ratio of Mn to Fe in FMO is about 1:1, and the molar ratio is FMO (1:1).
Adding ferrous sulfate solution and potassium permanganate solution according to the molar ratio of Mn to Fe of 1:0.1, 1:0.5, 1:1, 1:3 and 1:10 respectively, and preparing FMO (1:0.1), FMO (1:0.5), FMO (1:1), FMO (1:3) and FMO (1:10) under the same process conditions.
FIG. 1A shows MnO in the form of commercially available gamma crystals of a ferro-manganese composite metal oxide FMO prepared in example 1 of the present application 2 X-ray polycrystalline diffraction pattern of commercial ferroferric oxide type Fe oxide. It can be seen that both manganese oxide and iron oxide in FMO prepared in example 1 of the present application have no characteristic peaks of crystals and thus are amorphous. FIGS. 1B and 1C are respectively fine X-ray photoelectron spectra of iron and manganese in FMO, and according to the valence analysis of iron and manganese in FMO in FIGS. 1B and 1C, manganese oxide and iron oxide in FMO are mainly MnO 2 And Fe (Fe) 3 O 4 。
Example 2: iodide and fluoride removal effects of iron-manganese composite metal oxide FMO (1:0.5)
1g of the iron-manganese composite metal oxide FMO (1:0.5) prepared in example 1 was placed in a 1L iodine/fluorine removal device (stirring rate: 500 r/min) equipped with a stirrer, 1L of iodine-containing and fluorine-containing water (initial iodine ion concentration: 200. Mu.g/L, initial fluorine ion concentration: 0.1mmol/L (equivalent to 1.9 mg/L), 0.2mmol/L (equivalent to 3.8 mg/L), 5mmol/L (equivalent to 95 mg/L), and 10mmol/L (equivalent to 190 mg/L)) was introduced into the reaction device by a peristaltic pump, and after thoroughly mixing for 90min, the iodine ions and fluorine ion concentrations in the water were detected.
FIG. 2 shows the effect of removing iodide and fluoride simultaneously with FMO (1:0.5) of the iron-manganese composite metal oxide prepared in example 1 of the present application. It can be seen that the removal effect of FMO (1:0.5) on iodide decreased with increasing initial fluoride concentration, and that the removal effect of iodide decreased from 46.74% to 2.61% when the initial fluoride concentration increased from 1.9mg/L to 190 mg/L. The concentration of fluoride in general high iodine groundwater is about 1mg/L to 2mg/L, and the iodide removal effect is about 46% or more.
In addition, FMO (1:0.5) also has a higher fluoride removal effect, and the fluoride removal effect is slightly higher than that of iodide.
Example 3: effect of removing iodide and fluoride of iron-manganese composite metal oxide with different Mn/Fe molar ratio
1g of the iron-manganese composite metal oxide FMO (1:0.1), FMO (1:0.5), FMO (1:1), FMO (1:3) and FMO (1:10) prepared in example 1 were placed in a 1L iodine and fluorine removal device (stirring rate 500 r/min) with a stirrer, 1L of water containing iodine or fluorine ions and iodine and fluorine ions simultaneously (initial iodine ion concentration: 200. Mu.g/L and initial fluorine ion concentration: 3.8 mg/L) were introduced into the reaction device by a peristaltic pump, thoroughly mixed for 90min, and then discharged, and the iodine ion concentration and fluorine ion concentration in the water were detected.
FIG. 3 shows the iodide removal effect of the iron-manganese composite metal oxide FMO prepared in example 1 of the present application at different molar ratios when iodine is removed alone; FIG. 4 shows fluoride removal effects of separate fluorine removal of the iron-manganese composite metal oxide FMO prepared in example 1 of the present application.
It can be seen that the prepared FMO with different Mn/Fe molar ratios has good iodide removal effect, and the iodide removal effect can reach 78% after 90min of reaction under the condition that the Mn/Fe molar ratio is 1:0.5. In addition, the removal effect of FMO alone for removing fluoride can reach about 80%. The results also demonstrate that FMO is an effective iodine and fluorine scavenger.
Example 4: iodine morphology change of iron-manganese composite metal oxide FMO during separate iodine removal
1g of the iron-manganese composite metal oxide FMO (1:0.5) prepared in example 1 was placed in a 1L iodine fluoride removing device (stirring rate 500 r/min) with a stirrer, 1L of iodine ion-containing water (initial iodine ion concentration 156. Mu.g/L) was fed into the reaction device through a peristaltic pump, and after thoroughly mixing for 90min, the mixture was discharged, and the form concentration of iodine in the water was detected.
FIG. 5 shows the concentration change of iodine form when the iron-manganese composite metal oxide FMO (1:0.5) prepared in example 1 of the present application is used to remove iodide from water; FIG. 6 shows the solid phase iodine morphology change (XPS high resolution spectrum of iodine) after removal of iodide in water of the iron-manganese composite metal oxide FMO (1:0.5) prepared in example 1 of the present application.
It can be seen that during the removal of iodine from FMO, the concentration of iodide ions decreased with increasing reaction time from the initial 156.2. Mu.g/L to 53.5. Mu.g/L. At the same time, HOI hypoiodite (iodine is positive monovalent) slightly decreased after accumulation in the solution, indicating I - First oxidized by FMO to I 2 HOI, then adsorbed or oxidatively removed. Iodate ion IO is not detected in water 3 - (iodine is positively pentavalent), but in the solid phase iodine form of FIG. 6, it was detected that the FMO surface adsorbs I - 、I 2 、IO 3 - Isomorphous iodine, indicating I during FMO iodine removal - Is oxidized to I 2 after/HOI, further oxidation forms IO 3 - And adsorbed and removed.
The above results indicate that the iodine removal of FMO is performed by heterogeneous oxidation and adsorption, and that FMO has adsorption removal capacity for each iodine form.
Example 5: effect of iron oxide, manganese oxide and iron-manganese composite metal oxide FMO in removing iodine or fluorine
1g of the iron-manganese complex gold prepared in example 1 was respectivelyBelonging to oxide FMO (1:0.5), commercial ferroferric oxide type iron oxide and commercial gamma crystal form MnO 2 1L iodine or fluorine ion-containing water (initial iodine ion concentration is 200 mug/L or initial fluorine ion concentration is 3.8mg/L respectively) is put into a reaction device through a peristaltic pump in a 1L iodine or fluorine ion-removing device with a stirrer (stirring speed is 500 r/min), and the iodine ions and the fluorine ions in the water are detected after the water is fully mixed for 180 min.
FIGS. 7 and 8 show the iron-manganese composite metal oxide FMO (1:0.5), commercially available ferroferric oxide, and commercially available gamma-crystalline MnO prepared in example 1 of the present application 2 Wherein ferro-manganese oxide-iodide means FMO (1:0.5) removal of iodide alone, ferro-manganese oxide-fluoride means FMO (1:0.5) removal of fluoride alone, and the other lines are meant to be similar.
It can be seen that FMO has better removal effects on iodides and fluorides, the removal effect of the iodides can reach more than 90% after 180min of reaction, the removal effect of the fluorides is almost 100%, the removal effects are obviously higher than the removal effects of the iodides and the fluorides of the independent commercial iron oxides and the independent commercial manganese oxides, and the removal effects of the iodides and the fluorides of the FMO are higher than the sum of the removal effects of the iodides and the fluorides of the independent commercial iron oxides and the independent commercial manganese oxides (as shown in fig. 8), so that the capability of synergistic iodine or fluorine removal is obtained after the iron oxides and the manganese oxides are compounded in the embodiment of the application.
Example 6: regeneration removal effect after saturated adsorption of iodide or fluoride by ferromanganese composite metal oxide FMO 1g of ferromanganese composite metal oxide FMO (1:0.5) prepared in example 1 after saturated adsorption of iodide or fluoride was placed in a 1L regeneration device (stirring rate 500 r/min) with a stirrer, 1L regeneration solution (containing alkaline water, pH 9 to 11) was fed into the reaction device by peristaltic pump, and after thoroughly mixing for 24 hours, water iodide and fluoride concentration was detected. Then placing the regenerated iron-manganese composite metal oxide FMO into a 1L iodine/fluorine removing device (stirring speed is 500 r/min) with a stirrer, introducing 1L iodine-containing or fluorine-containing water (initial iodine ion concentration is 200 mug/L, initial fluorine ion concentrations are 3.8mg/L respectively) into a reaction device through a peristaltic pump, fully mixing for 300min, and then flowing out to detect the iodine ion concentration and the fluorine ion concentration of water.
FIG. 9 shows the effect of removing iodides or fluorides of the iron-manganese composite metal oxide FMO (1:0.5) prepared in example 1 of the present application after regeneration with regeneration solutions of different pH values. It can be seen that the regenerated FMO has good removal effect on iodide and fluoride, and the removal effect of iodide and fluoride can reach more than 80% after 180min of reaction, which indicates that the iron-manganese oxide FMO prepared by the embodiment of the application has good regeneration capability.
Although the embodiments disclosed in the present application are described above, the embodiments are only used for facilitating understanding of the present application, and are not intended to limit the present application. Any person skilled in the art to which this application pertains will be able to make any modifications and variations in form and detail of implementation without departing from the spirit and scope of the disclosure, but the scope of the application is still subject to the scope of the claims appended hereto.
Claims (15)
1. The iodine remover is characterized by comprising a ferro-manganese composite metal oxide, wherein the ferro-manganese composite metal oxide is a composite metal oxide of manganese oxide and ferric oxide.
2. The iodine scavenger according to claim 1, wherein in the iron-manganese composite metal oxide, a molar ratio of Mn in the manganese oxide to Fe in the iron oxide is 1 (0.1 to 10).
3. The iodine scavenger according to claim 1 or 2, wherein the manganese oxide and the iron oxide in the iron-manganese composite metal oxide are both amorphous and amorphous.
4. The iodine scavenger according to claim 1 or 2, wherein the manganese oxide comprises MnO 2 The iron oxide includes Fe 3 O 4 。
5. The defluorinating agent is characterized by comprising a ferro-manganese composite metal oxide, wherein the ferro-manganese composite metal oxide is a composite metal oxide of manganese oxide and ferric oxide.
6. The fluorine removal agent according to claim 5, wherein in the iron-manganese composite metal oxide, a molar ratio of Mn in the manganese oxide to Fe in the iron oxide is 1 (0.1 to 10).
7. The fluorine removal agent according to claim 5 or 6, wherein both of the manganese oxide and the iron oxide in the iron-manganese composite metal oxide are amorphous.
8. The fluorine scavenger according to claim 5 or 6, wherein the manganese oxide comprises MnO 2 The iron oxide includes Fe 3 O 4 。
9. The application of the iron-manganese composite metal oxide is characterized by comprising the steps of adopting the iron-manganese composite metal oxide to remove iodine in water, or remove fluorine in water, or remove iodine and fluorine in water; the ferro-manganese composite metal oxide is a composite metal oxide of manganese oxide and ferric oxide.
10. Use according to claim 9, characterized in that in the ferro-manganese complex metal oxide the molar ratio of Mn in the manganese oxide to Fe in the iron oxide is 1 (0.1 to 10).
11. The use according to claim 10, wherein the manganese oxide and the iron oxide in the iron-manganese composite metal oxide are both amorphous and amorphous.
12. Use according to claim 10, characterized in thatThe manganese oxide includes MnO 2 The iron oxide includes Fe 3 O 4 。
13. Use according to any one of claims 9 to 12, comprising:
adding the iron-manganese composite metal oxide into water to be treated containing any one or two of iodine and fluorine, stirring until the treated water meets at least one of the following conditions, and performing solid-liquid separation:
a) The iodide concentration is less than or equal to 100 mug/L;
b) The concentration of fluoride is less than or equal to 1mg/L.
14. The use of claim 13, further comprising either or both of:
c) When the iodine removal effect does not reach the expected value, regulating the pH value of the iron-manganese composite metal oxide to regenerate the iron-manganese composite metal oxide;
d) And when the fluorine removal effect does not reach the expected value, regenerating the ferro-manganese composite metal oxide by adopting a method of adding an aluminum-containing coagulant into the system.
15. The use according to claim 13, wherein 1L of the water to be treated is added with the ferro-manganese complex metal oxide in an amount of 0.5g to 1.5g;
the initial iodide ion concentration in the water to be treated is not higher than 300 mug/L, and/or the initial fluoride ion concentration is not higher than 4mg/L.
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