CN113181928A - Modification method of iron-doped birnessite, modified iron-doped birnessite and application of modified iron-doped birnessite - Google Patents
Modification method of iron-doped birnessite, modified iron-doped birnessite and application of modified iron-doped birnessite Download PDFInfo
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- CN113181928A CN113181928A CN202011511933.9A CN202011511933A CN113181928A CN 113181928 A CN113181928 A CN 113181928A CN 202011511933 A CN202011511933 A CN 202011511933A CN 113181928 A CN113181928 A CN 113181928A
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- 238000002715 modification method Methods 0.000 title claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 36
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 27
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 27
- 235000002867 manganese chloride Nutrition 0.000 claims description 27
- 239000011565 manganese chloride Substances 0.000 claims description 27
- 229940099607 manganese chloride Drugs 0.000 claims description 27
- 229960002089 ferrous chloride Drugs 0.000 claims description 24
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 56
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 27
- 239000010865 sewage Substances 0.000 abstract description 25
- 230000003647 oxidation Effects 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- -1 nitrate ions Chemical class 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 abstract description 5
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 12
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 238000005273 aeration Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATWXRSQXGJLIIR-UHFFFAOYSA-N O.[Na].[Mn] Chemical compound O.[Na].[Mn] ATWXRSQXGJLIIR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- JLRMNCKQXMSQAR-UHFFFAOYSA-L [Na+].[Mn+2].[O-]S([O-])(=O)=O Chemical compound [Na+].[Mn+2].[O-]S([O-])(=O)=O JLRMNCKQXMSQAR-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- DQVJNIURAJAIEY-UHFFFAOYSA-N sodium;manganese(2+) Chemical compound [Na+].[Mn+2] DQVJNIURAJAIEY-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/14—NH3-N
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/15—N03-N
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of sewage treatment agents, in particular to a modification method of iron-doped birnessite, modified iron-doped birnessite and application thereof. The preparation method comprises the following preparation steps: preparing iron-doped birnessite; pressing the prepared iron-doped birnessite into a cake shape, dropwise adding hydrogen peroxide onto the cake-shaped iron-doped birnessite, reacting, washing, and performing suction filtration to obtain the modified iron-doped birnessite. The invention aims to provide an iron-doped birnessite modification method, a modified iron-doped birnessite and application thereof, and the technical problems that an iron-doped birnessite catalyst in the prior art has no selectivity on ammonia nitrogen oxidation, and an oxidation product is nitrate ions and can not be converted into nitrogen gas, so that a water body brings new pollutants, and total nitrogen is difficult to reach a discharge standard are solved through the iron-doped birnessite modification method.
Description
Technical Field
The invention relates to the technical field of sewage treatment agents, in particular to a modification method of iron-doped birnessite, modified iron-doped birnessite and application thereof.
Background
With the continuous development of society, the problem of water pollution has made a serious threat to national economy and the living environment of people. The ammonia nitrogen is used as a main pollution index, and the content of the ammonia nitrogen exceeds the standard, so that the concentration of dissolved oxygen in water is reduced, the water body is blacked and smelly, the water quality is reduced, and the survival of aquatic animals and plants is damaged, so that the reduction of the ammonia nitrogen is one of key ways for ensuring the improvement of the water quality. The catalytic oxidation method is a novel and efficient water treatment technology which is developed rapidly in recent years, and mainly comprises the step of catalytically oxidizing ammonia nitrogen in sewage at normal temperature and normal pressure by contacting wastewater with the surface of a catalyst in an oxygen-containing environment. The technical core of the catalytic oxidation deamination lies in a catalyst with excellent performance, and the catalyst needs to have good selective oxidation capacity on ammonia nitrogen and ensure that an oxidation product is nitrogen while ensuring high activity and good stability.
Manganese oxides have been widely studied for their structural diversity and specificity of properties, among which birnessite type manganese dioxide is a manganese oxide composed of MnO6The layered metal oxide composed of octahedral basic units has catalytic activity superior to that of manganese dioxide with other crystal structure, and iron is doped into birnessite to substitute trivalent manganese ion in octahedron in a similar manner so as to obtain lattice parameterThe catalytic activity of the catalyst is further improved by a slight change. The iron-doped birnessite has become a catalytic material with great development potential due to high activity and good stability, but the iron-doped birnessite catalyst has no selectivity on the oxidation of ammonia nitrogen, and the oxidation product is nitrate ions which can not be converted into nitrogen gas, so that new pollutants are brought by a water body, and the total nitrogen can hardly reach the discharge standard.
Therefore, in order to solve the above problems, the present invention urgently needs to provide a method for modifying iron-doped birnessite, a modified iron-doped birnessite and applications thereof.
Disclosure of Invention
The invention aims to provide an iron-doped birnessite modification method, a modified iron-doped birnessite and application thereof, and the technical problems that an iron-doped birnessite catalyst in the prior art has no selectivity on ammonia nitrogen oxidation, and an oxidation product is nitrate ions and cannot be converted into nitrogen gas, so that a water body brings new pollutants, and total nitrogen hardly reaches a discharge standard are solved through the iron-doped birnessite modification method.
The invention provides a modification method of iron-doped birnessite, which comprises the following preparation steps:
preparing iron-doped birnessite;
pressing the prepared iron-doped birnessite into a cake shape, dropwise adding hydrogen peroxide onto the cake-shaped iron-doped birnessite, reacting, washing, and performing suction filtration to obtain the modified iron-doped birnessite.
Preferably, the mass ratio of the iron-doped birnessite to hydrogen peroxide is 1-3: 1.
Preferably, the mass ratio of the iron-doped birnessite to hydrogen peroxide is 3: 1.
Preferably, the mass fraction of hydrogen peroxide is 30%.
Preferably, the particle size range of the obtained modified iron-doped birnessite is 300nm-900 nm.
Preferably, dropwise adding hydrogen peroxide into the cake-shaped iron-doped birnessite, stirring, sealing the beaker after dropwise adding, standing for 20-60min, and performing suction filtration and washing after standing to obtain the modified iron-doped birnessite.
Preferably, the hydrogen peroxide is added into the cake-shaped iron-doped birnessite dropwise and stirred, and after the dropwise addition is finished, the beaker is sealed and kept stand for 50 min.
Preferably, the preparation step of the iron-doped birnessite comprises the following steps:
weighing manganese chloride and ferrous chloride, and adding the manganese chloride and the ferrous chloride into deionized water for dissolving to obtain a mixed solution of the manganese chloride and the ferrous chloride;
adjusting the acidity of the mixed solution of manganese chloride and ferrous chloride by using hydrochloric acid, wherein the pH value of the mixed solution of manganese chloride and ferrous chloride is 2-3;
and (2) dropwise adding 0.5-2mol/L potassium permanganate solution into the mixed solution of manganese chloride and ferrous chloride, wherein the potassium permanganate: manganese chloride: the molar ratio of ferric chloride is 3:2: 2; stirring and reacting for a certain time, and filtering and washing to obtain the iron-doped birnessite.
The invention also provides the modified iron-doped birnessite obtained by the method for modifying the iron-doped birnessite.
The invention also provides an application of the modified iron-doped birnessite.
Compared with the prior art, the modification method of the iron-doped birnessite, the modified iron-doped birnessite and the application thereof provided by the invention have the following advantages:
1. according to the modification method of the iron-doped birnessite, hydrogen peroxide is adopted to modify the iron-doped birnessite, the surface of the modified iron-doped birnessite has rich oxygen species, the modified iron-doped birnessite has high-efficiency catalytic oxidation capacity and strong stability, 0-100mg/L ammonia nitrogen can be degraded only through aeration without adding any chemical agent, the operation is convenient and fast, the energy consumption is low, the cost is saved, the stability of the produced water can be always kept in the long-term operation process, and the performance attenuation does not occur.
2. The modification method of the iron-doped birnessite provided by the invention is characterized in that hydrogen peroxide is used as a modifier to modify the iron-doped birnessite, so that the species and the content of active oxygen on the surface of the iron-doped birnessite are changed, an ammonia nitrogen oxidation path is changed, an ammonia nitrogen oxidation product is converted into nitrite ions from nitrate ions, the nitrite ions further perform a centering reaction with ammonium ions in a system in which the iron-doped birnessite exists, the conversion of ammonia nitrogen into nitrogen is realized, no nitrate nitrogen and nitrite nitrogen are accumulated in the whole process, and the modification method is green and environment-friendly and has no secondary pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a block diagram of the steps of the modification method of iron-doped birnessite according to the present invention;
fig. 2 is an electron microscope scanning image of the iron-doped birnessite and the modified iron-doped birnessite according to the present invention.
FIG. 3 shows that the water of the municipal sewage treatment plant in Beijing Cui lake is used as experimental water to study the change of ammonia nitrogen and total nitrogen in inlet water and produced water along with the increase of the treated water.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood in specific cases to those skilled in the art.
As shown in fig. 1, the invention provides a modification method of iron-doped birnessite, which comprises the following preparation steps:
s101) preparing iron-doped birnessite;
s102) pressing the prepared iron-doped birnessite into a cake shape, dropwise adding hydrogen peroxide onto the cake-shaped iron-doped birnessite, reacting, washing, and performing suction filtration to obtain the modified iron-doped birnessite.
Specifically, the mass ratio of the iron-doped birnessite to the hydrogen peroxide is 1-3: 1.
Specifically, the mass ratio of the iron-doped birnessite to hydrogen peroxide is 3: 1.
Specifically, the mass fraction of hydrogen peroxide was 30%.
Specifically, the particle size range of the obtained modified iron-doped birnessite is 300nm-900 nm.
Specifically, dropwise adding hydrogen peroxide into cake-shaped iron-doped birnessite, stirring, sealing the beaker after dropwise adding, standing for 20-60min, and performing suction filtration and washing after standing to obtain the modified iron-doped birnessite.
Specifically, hydrogen peroxide is added into the cake-shaped iron-doped birnessite dropwise and stirred, and after the dropwise addition is finished, the beaker is sealed and kept stand for 50 min.
Specifically, the preparation method of the iron-doped birnessite comprises the following steps:
weighing manganese chloride and ferrous chloride, and adding the manganese chloride and the ferrous chloride into deionized water for dissolving to obtain a mixed solution of the manganese chloride and the ferrous chloride;
adjusting the acidity of the mixed solution of manganese chloride and ferrous chloride by using hydrochloric acid, wherein the pH value of the mixed solution of manganese chloride and ferrous chloride is 2-3;
and (2) dropwise adding 0.5-2mol/L potassium permanganate solution into the mixed solution of manganese chloride and ferrous chloride, wherein the potassium permanganate: manganese chloride: the molar ratio of ferric chloride is 3:2: 2; stirring and reacting for a certain time, and filtering and washing to obtain the iron-doped birnessite.
The invention also provides the modified iron-doped birnessite obtained by the method for modifying the iron-doped birnessite.
The invention also provides an application of the modified iron-doped birnessite. The modified iron-doped birnessite has abundant oxygen species on the surface, has high-efficiency catalytic oxidation capacity and high stability, can degrade 0-100mg/L ammonia nitrogen only by aeration without adding any chemical agent, is convenient to operate, has low energy consumption and saves cost, and can always keep the stability of water production without performance attenuation in the long-term operation process.
According to the invention, the hydrogen peroxide is used as a modifier to modify the iron-doped birnessite, so that the species and the content of active oxygen on the surface of the iron-doped birnessite are changed, the ammonia nitrogen oxidation way is changed when the iron-doped birnessite is used for sewage treatment, the ammonia nitrogen oxidation product is converted into nitrite ions from nitrate ions, and in a system in which the iron-doped birnessite exists, the nitrite ions further perform a centering reaction with ammonium ions, so that the conversion of ammonia nitrogen into nitrogen is realized, and the whole process has no accumulation of nitrate nitrogen and nitrite nitrogen, is green and environment-friendly, and has no secondary pollution.
The sewage treatment mechanism of the modified iron-doped birnessite is as follows:
1) oxygen generated from hydrogen peroxide is adsorbed onto the surface of the iron-doped birnessite, electrons on the surface of the iron-doped birnessite are transferred to the adsorbed oxygen molecules, and then O with negative charges is generated2 -Is dissociated into O-The specific process is as follows:
O2 (dissolved oxygen)→O2 (adsorbing oxygen)(adsorption Process)
O2 (adsorbing oxygen)+e-→O2 -(Electron transfer Process)
O2 -+e-→2O-(dissociation process)
2) Absorbing ammonium ions to the surface of the iron-doped birnessite;
3) ammonium ions adsorbed on the surface of the modified iron-doped birnessite are oxidized by the modified iron-doped birnessite to strip hydrogen, the content of oxygen species adsorbed on the surface of the modified iron-doped birnessite is increased, the number of captured N is increased, the stability of the oxidation species is deteriorated, the oxidation degree is lowered, and the modified product is converted from nitrate radical into nitrite radical;
4) when the modified iron-doped birnessite oxidizes ammonium ions, trivalent manganese and quadrivalent manganese in self crystal lattices are reduced into bivalent manganese; oxidizing bivalent manganese into trivalent manganese and quadrivalent manganese under the action of dissolved oxygen, and restoring the structure of the modified iron-doped birnessite;
5) the newly generated nitrite and the unreacted ammonium radical in the water body are subjected to a centering reaction under the catalysis of the modified iron-doped sodium manganese sulfate to generate N2And (4) discharging the system.
2Mn5++(O-/O2 -/O2 2-)Adsorption of nitrogen+NH4 +→2Mn2++NO2 -+4H+
2Mn3++(O-/O2 -/O2 2-)Adsorption of nitrogen+NH4 +→2Mn2++NO2 -+4H+
NH4 ++NO2 -→N2+2H2O
Example one
Preparing modified iron-doped birnessite (I):
preparing 900mL of 0.5mol/L potassium permanganate solution;
preparing 1L of mixed solution containing 0.35mol/L of manganese chloride and 0.35mol/L of ferrous chloride, and adjusting the pH value of the mixed solution to 2 by using 1M hydrochloric acid;
slowly dripping the prepared potassium permanganate solution into the mixed solution of manganese chloride and ferrous chloride, continuing stirring for 2 hours after finishing dripping, sealing the beaker after finishing dripping, standing for 50min, filtering after complete reaction, and washing with deionized water to obtain the iron-doped birnessite.
Weighing 80g of iron-doped birnessite, dropwise adding 80mL of 30% hydrogen peroxide onto the surface of the iron-doped birnessite, continuously stirring in the dropwise adding process, sealing for 2 hours after the dropwise adding is finished, washing, and filtering to obtain the modified iron-doped birnessite (I).
The particle size of the obtained modified iron-doped birnessite is 300nm-500 nm.
In fig. 2, a1 represents the iron-doped birnessite before modification, and a2 represents the modified iron-doped birnessite (one).
From SEM picture, it can be seen that the iron-doped birnessite (I) has more fold structures, and after being modified by hydrogen peroxide, the fold structures slightly collapse but still have sparse and fluffy surface structures, so that more adsorption and reaction sites are provided for catalysis of ammonia nitrogen.
The modified iron-doped birnessite (I) is applied to sewage treatment:
as shown in Table 1, the actual sewage of the Beijing Miyun municipal sewage plant is used as experimental water, and the initial ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen concentrations of the experimental water are respectively 56mg/L, 0.6mg/L, 1.2mg/L and 58 mg/L.
And (3) placing the modified iron-doped birnessite (I) into sewage, stirring and continuously aerating, and sampling at intervals to measure the contents of ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen in the solution.
As shown in the table 1, ammonia nitrogen and total nitrogen are reduced along with the increase of aeration time, the content of nitrite nitrogen is increased firstly and then reduced, and the concentration of nitrate nitrogen is basically unchanged in the whole operation process; this phenomenon indicates that ammonia nitrogen does not have NO in the oxidation process by using the catalyst3 -The product is mainly nitrite, nitrite can react with ammonium during operation to generate nitrogen, and the operation lasts for 20 hours, so that the total nitrogen is reduced to below 1 mg/L.
As shown in figure 3, the water body of a municipal sewage treatment plant in Beijing Cui lake is used as experimental water, the initial ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen concentration of the experimental water are respectively 62mg/L, 0.4mg/L, 0.8mg/L and 64mg/L, the modified iron-doped birnessite is added into the experimental water, the contact time is 40min, continuous aeration is carried out, the ammonia nitrogen and the total nitrogen in produced water are below 1mg/L, and the performance attenuation phenomenon still does not occur in the continuous treatment of 200L of wastewater, which shows that the ammonia nitrogen in the wastewater can be continuously and stably treated by using the modified iron-doped birnessite (I), the produced water meets the requirements of III-class water on the ground surface, and the modified iron-doped birnessite (I) can be applied to the actual wastewater treatment in a large scale.
Table 1 detection data of modified iron-doped sodium manganese (ii) water obtained in the first example on actual sewage of beijing dense cloud municipal sewage plant
Example two
Preparing modified iron-doped birnessite (II):
preparing 900mL of 0.5mol/L potassium permanganate solution;
preparing 1L of mixed solution containing 0.35mol/L of manganese chloride and 0.35mol/L of ferrous chloride, and adjusting the pH value of the mixed solution to 2 by using 1M hydrochloric acid;
slowly dripping the prepared potassium permanganate solution into the mixed solution of manganese chloride and ferrous chloride while stirring, continuing stirring for 2 hours after finishing dripping, sealing the beaker after finishing dripping, standing for 50min, filtering after reaction is finished, and washing with deionized water to obtain the iron-doped birnessite.
Weighing 80g of iron-doped birnessite, dropwise adding 150mL of 30% hydrogen peroxide onto the surface of the iron-doped birnessite, continuously stirring in the dropwise adding process, sealing for 2 hours after the dropwise adding is finished, washing, and filtering to obtain modified iron-doped birnessite (II).
The particle size of the obtained modified iron-doped birnessite is 300nm-500 nm.
The modified iron-doped birnessite (II) is applied to sewage treatment:
as shown in Table 2, the actual sewage of the Beijing Miyun municipal sewage plant is used as the experimental water, and the initial ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen concentrations of the experimental water are respectively 56mg/L, 0.6mg/L, 1.2mg/L and 58 mg/L.
And (3) placing the modified iron-doped birnessite (II) into sewage, stirring and continuously aerating, and sampling at intervals to determine the contents of ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen in the solution.
As shown in Table 2, ammonia nitrogen and total nitrogen both decrease with the increase of aeration time, the content of nitrite nitrogen tends to increase first and then decrease, and the concentration of nitrate nitrogen is basically unchanged in the whole operation process; this phenomenon indicates that, using modified iron-doped birnessite (II), ammonia nitrogen does not have NO in the oxidation process3 -And (2) the product is mainly nitrite, nitrite can react with ammonium during operation to generate nitrogen, the total nitrogen can be reduced to below 1mg/L after operation for 23h, and compared with the first case, the efficiency is reduced along with the reduction of the mass ratio of the iron-doped birnessite to the hydrogen peroxide, the efficiency is slightly reduced, but no secondary pollution exists, and the method has practical application prospect.
Table 2 detection data of modified iron-doped sodium manganese hydrate obtained in example two on actual sewage of beijing dense cloud municipal sewage plant
EXAMPLE III
Preparing modified iron-doped birnessite (III):
preparing 900mL of 0.5mol/L potassium permanganate solution;
preparing 1L of mixed solution containing 0.35mol/L of manganese chloride and 0.35mol/L of ferrous chloride, and adjusting the pH value of the mixed solution to 2 by using 1M hydrochloric acid;
slowly dripping the prepared potassium permanganate solution into the mixed solution of manganese chloride and ferrous chloride, continuing stirring for 2 hours after finishing dripping, sealing the beaker after finishing dripping, standing for 50min, filtering after finishing reaction, and washing with deionized water to obtain the iron-doped birnessite.
Weighing 80g of iron-doped birnessite, dropwise adding 200mL of 30% hydrogen peroxide onto the surface of the iron-doped birnessite, continuously stirring in the dropwise adding process, sealing for 2 hours after the dropwise adding is finished, washing, and filtering to obtain modified iron-doped birnessite (III).
The particle size of the obtained modified iron-doped birnessite is 300nm-500 nm.
The modified iron-doped birnessite (III) is applied to sewage treatment:
as shown in Table 3, the actual sewage of the Beijing Miyun municipal sewage plant is used as the experimental water, and the initial ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen concentrations of the experimental water are respectively 56mg/L, 0.6mg/L, 1.2mg/L and 58 mg/L.
And (3) placing the modified iron-doped birnessite (III) ore into sewage, stirring and continuously aerating, and sampling at intervals to determine the contents of ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen in the solution.
As shown in Table 3, ammonia nitrogen and total nitrogen both decrease with the increase of aeration time, the content of nitrite nitrogen tends to increase first and then decrease, and the concentration of nitrate nitrogen is basically unchanged in the whole operation process; this phenomenon indicates that ammonia nitrogen does not have NO in the oxidation process by using the catalyst3 -The product is mainly nitrite, nitrite can react with ammonium radical during operation to generate nitrogen, the operation lasts for 26h,the total nitrogen is reduced to be below 1mg/L, the ammonia nitrogen degradation efficiency is reduced along with the reduction of the mass ratio of the iron-doped birnessite to the hydrogen peroxide, but no secondary pollution is caused, the total nitrogen can be reduced to be below 1mg/L by using the catalyst, and the catalyst is green and environment-friendly and has practical application prospect.
Table 3 detection data of modified iron-doped sodium manganese hydrate obtained in example three on actual sewage of beijing dense cloud municipal sewage plant
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A modification method of iron-doped birnessite is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
preparing iron-doped birnessite;
pressing the prepared iron-doped birnessite into a cake shape, dropwise adding hydrogen peroxide onto the cake-shaped iron-doped birnessite, reacting, washing, and performing suction filtration to obtain the modified iron-doped birnessite.
2. The method for modifying iron-doped birnessite according to claim 1, wherein the method comprises the following steps: the mass ratio of the iron-doped birnessite to the hydrogen peroxide is 1-3: 1.
3. The method for modifying iron-doped birnessite according to claim 2, wherein the method comprises the following steps: the mass ratio of the iron-doped birnessite to the hydrogen peroxide is 3: 1.
4. The method for modifying iron-doped birnessite according to claim 1, wherein the method comprises the following steps: the mass fraction of hydrogen peroxide was 30%.
5. The method for modifying iron-doped birnessite according to claim 1, wherein the method comprises the following steps: the particle size range of the obtained modified iron-doped birnessite is 300nm-900 nm.
6. The method for modifying iron-doped birnessite according to claim 1, wherein the method comprises the following steps: dropwise adding hydrogen peroxide into the cake-shaped iron-doped birnessite, stirring, sealing the beaker after dropwise adding, standing for 20-60min, and performing suction filtration and washing after standing to obtain the modified iron-doped birnessite.
7. The method for modifying iron-doped birnessite according to claim 6, wherein the method comprises the following steps: dropwise adding hydrogen peroxide into the cake-shaped iron-doped birnessite, stirring, sealing the beaker after dropwise adding, and standing for 50 min.
8. The method for modifying iron-doped birnessite according to claim 1, wherein the method comprises the following steps: the preparation method of the iron-doped birnessite comprises the following steps of:
weighing manganese chloride and ferrous chloride, and adding the manganese chloride and the ferrous chloride into deionized water for dissolving to obtain a mixed solution of the manganese chloride and the ferrous chloride;
adjusting the acidity of the mixed solution of manganese chloride and ferrous chloride by using hydrochloric acid, wherein the pH value of the mixed solution of manganese chloride and ferrous chloride is 2-3;
and (2) dropwise adding 0.5-2mol/L potassium permanganate solution into the mixed solution of manganese chloride and ferrous chloride, wherein the potassium permanganate: manganese chloride: the molar ratio of ferric chloride is 3:2: 2; stirring and reacting for a certain time, and filtering and washing to obtain the iron-doped birnessite.
9. A modified iron-doped birnessite obtained based on the iron-doped birnessite modification method of any one of claims 1 to 8.
10. Use of the modified iron-doped birnessite according to claim 9.
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