CN113181928B - Iron-doped birnessite modification method, modified iron-doped birnessite and application thereof - Google Patents
Iron-doped birnessite modification method, modified iron-doped birnessite and application thereof Download PDFInfo
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- 238000002715 modification method Methods 0.000 title claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 33
- 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
- 229940099607 manganese chloride Drugs 0.000 claims description 27
- 235000002867 manganese chloride Nutrition 0.000 claims description 27
- 239000011565 manganese chloride Substances 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
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 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 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
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 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 59
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 30
- 239000010865 sewage Substances 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- -1 nitrate ions Chemical class 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 abstract description 6
- 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
- 230000003647 oxidation Effects 0.000 description 17
- 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 9
- 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 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 150000002505 iron Chemical class 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 8
- 238000001179 sorption measurement Methods 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
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 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
- 239000010841 municipal wastewater Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- GFORUURFPDRRRJ-UHFFFAOYSA-N [Na].[Mn] Chemical compound [Na].[Mn] GFORUURFPDRRRJ-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
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 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
- 238000006467 substitution reaction Methods 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002474 experimental method Methods 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
- 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003911 water pollution Methods 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
- 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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- Chemical & Material Sciences (AREA)
- 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 an iron-doped birnessite modification method, 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, dripping hydrogen peroxide onto the cake-shaped iron-doped birnessite, and washing and suction filtering after the reaction to obtain the modified iron-doped birnessite. The invention aims to provide a modification method of iron-doped birnessite, modified iron-doped birnessite and application thereof, and the technical problems that an iron-doped birnessite catalyst does not have selectivity on oxidization of ammonia nitrogen, an oxidized product is nitrate ions and cannot be converted into nitrogen, so that new pollutants are brought to a water body and total nitrogen is difficult to reach emission standards are solved through the proposal of the modification method of the iron-doped birnessite.
Description
Technical Field
The invention relates to the technical field of sewage treatment agents, in particular to an iron-doped birnessite modification method, modified iron-doped birnessite and application thereof.
Background
With the continuous development of society, the water pollution problem has become a serious threat to national economy and people living environment. Ammonia nitrogen is used as a main pollution index, and the ammonia nitrogen content exceeds the standard, so that the concentration of dissolved oxygen in water is reduced, the water body is blackened and odorous, the water quality is reduced, the survival of aquatic animal plants is endangered, and therefore, the reduction of ammonia nitrogen is one of key ways for ensuring the improvement of the water body quality. The catalytic oxidation method is a novel high-efficiency water treatment technology which is developed rapidly in recent years, and is mainly a method for catalytic oxidation of ammonia nitrogen in sewage under normal temperature and normal pressure through contact of wastewater and the surface of a catalyst in an oxygen-containing environment, and the method has the advantages of high oxidation efficiency, no need of secondary treatment, no use method and no secondary pollution, and has obvious competitive advantages in economy and technology. The technical core of the catalytic oxidation deamination is that the catalyst with excellent performance has high activity and good stability, and meanwhile, the catalyst needs to have good selective oxidizing capability for ammonia nitrogen, so that the oxidation product is nitrogen.
Manganese oxides have been widely studied for their structural diversity and specificity of properties, in which birnessite type manganese dioxide is a type of manganese oxide composed of MnO 6 The layered metal oxide composed of octahedral basic units has catalytic activity superior to manganese dioxide with other crystal forms, and doping iron into birnessite can further improve the catalytic activity by slightly changing lattice parameters through substitution with trivalent manganese ions in octahedron. Iron doped birnessite has high activity and good stability, and becomes a catalytic material with development potential, but the iron doped birnessite catalyst has no selectivity on the oxidation of ammonia nitrogen, and an oxidation product is nitrate ions and cannot be converted into nitrogen, so that new pollutants are brought to a water body, and the total nitrogen is difficult to reach the emission standard.
Therefore, in order to solve the above problems, the present invention is needed to provide a modification method of iron-doped birnessite, modified iron-doped birnessite and application thereof.
Disclosure of Invention
The invention aims to provide a modification method of iron-doped birnessite, modified iron-doped birnessite and application thereof, and the technical problems that an iron-doped birnessite catalyst does not have selectivity on oxidization of ammonia nitrogen, an oxidized product is nitrate ions and cannot be converted into nitrogen, so that new pollutants are brought to a water body and total nitrogen is difficult to reach emission standards are solved through the proposal of the modification method of the iron-doped birnessite.
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, dripping hydrogen peroxide onto the cake-shaped iron-doped birnessite, reacting, washing, and suction filtering to obtain the modified iron-doped birnessite.
Preferably, the mass ratio of the iron-doped birnessite to the hydrogen peroxide is 1-3:1.
Preferably, the mass ratio of the iron-doped birnessite to the hydrogen peroxide is 3:1.
Preferably, the mass fraction of hydrogen peroxide is 30%.
Preferably, the particle size of the resulting modified iron-doped birnessite is in the range of 300nm to 900nm.
Preferably, the hydrogen peroxide is added into the cake-shaped iron-doped birnessite dropwise and stirred, after the dripping is finished, the beaker is sealed, the mixture is kept stand for 20 to 60 minutes, and after the standing is finished, the suction filtration and the washing are carried out to obtain the modified iron-doped birnessite.
Preferably, hydrogen peroxide is added dropwise to the cake-shaped iron-doped birnessite and stirred, and after the addition is completed, the beaker is sealed and allowed to stand for 50 minutes.
Preferably, the preparation steps of the iron-doped birnessite include:
weighing manganese chloride and ferrous chloride, and adding the manganese chloride and the ferrous chloride into deionized water for dissolution to obtain a manganese chloride and ferrous chloride mixed solution;
hydrochloric acid is adopted to adjust the acidity of the mixed solution of manganese chloride and ferrous chloride, and the pH value of the mixed solution of manganese chloride and ferrous chloride is 2-3;
dropwise adding 0.5-2mol/L potassium permanganate solution into manganese chloride and ferrous chloride mixed solution, wherein potassium permanganate: manganese chloride: the molar ratio of the ferric chloride is 3:2:2; and (3) after stirring and reacting for a certain time, filtering and washing to obtain the iron doped birnessite.
The invention also provides a modified iron-doped birnessite obtained based on the iron-doped birnessite modification method.
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 steps:
1. according to the method for modifying the iron-doped birnessite, the hydrogen peroxide is adopted to modify the iron-doped birnessite, the surface of the modified iron-doped birnessite has rich oxygen species, high-efficiency catalytic oxidation capability is achieved, the stability is high, no chemical agent is needed to be added, the ammonia nitrogen of 0-100mg/L can be degraded only through aeration, the operation is convenient and fast, the energy consumption is low, the cost is saved, the stability of water production can be kept all the time in the long-term operation process, and no performance attenuation occurs.
2. According to the method for modifying the iron-doped birnessite, the hydrogen peroxide is used as a modifier to modify the iron-doped birnessite, so that the surface active oxygen species and the content of the iron-doped birnessite are changed, the method is used for sewage treatment, an ammonia nitrogen oxidation path is changed, an 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 react with ammonium ions in a centering manner, so that the conversion of ammonia nitrogen into nitrogen is realized, no nitrate nitrogen and nitrite nitrogen are accumulated in the whole process, and the method is environment-friendly and free of 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 that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block diagram of steps of a method for modifying iron-doped birnessite according to the present invention;
FIG. 2 is an electron microscope scan of iron-doped birnessite and modified iron-doped birnessite according to the present invention;
fig. 3 is a diagram of the invention, which is to study the change situation of inflow water, ammonia nitrogen produced in water and total nitrogen along with the increase of the treated water amount by using the water body of the municipal sewage treatment plant in the Beijing green lake as experimental water.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific 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 explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill 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, dripping hydrogen peroxide on the cake-shaped iron-doped birnessite, and obtaining the modified iron-doped birnessite after reaction, washing and suction filtration.
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 the hydrogen peroxide is 3:1.
Specifically, the mass fraction of hydrogen peroxide was 30%.
Specifically, the particle size of the obtained modified iron-doped birnessite is 300-900 nm.
Specifically, dropwise adding hydrogen peroxide into cake-shaped iron-doped birnessite, stirring, sealing a beaker after the dropwise adding is finished, standing for 20-60min, and carrying out suction filtration and washing after the standing is finished to obtain the modified iron-doped birnessite.
Specifically, hydrogen peroxide is added into cake-shaped iron-doped birnessite dropwise and stirred, and after the addition, the beaker is sealed and kept stand for 50min.
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 dissolution to obtain a manganese chloride and ferrous chloride mixed solution;
hydrochloric acid is adopted to adjust the acidity of the mixed solution of manganese chloride and ferrous chloride, and the pH value of the mixed solution of manganese chloride and ferrous chloride is 2-3;
dropwise adding 0.5-2mol/L potassium permanganate solution into manganese chloride and ferrous chloride mixed solution, wherein potassium permanganate: manganese chloride: the molar ratio of the ferric chloride is 3:2:2; and (3) after stirring and reacting for a certain time, filtering and washing to obtain the iron doped birnessite.
The invention also provides a modified iron-doped birnessite obtained based on the iron-doped birnessite modification method.
The invention also provides an application of the modified iron-doped birnessite. The surface of the iron-doped birnessite modified by hydrogen peroxide has rich oxygen species, has high-efficiency catalytic oxidation capability and strong stability, does not need to add any chemical agent, can degrade ammonia nitrogen of 0-100mg/L only by aeration, is convenient to operate, has low energy consumption and saves cost, can always keep the stability of water production in the long-term operation process, and has no performance attenuation.
According to the invention, hydrogen peroxide is used as a modifier to modify the iron-doped birnessite, so that the surface active oxygen species and the content of the iron-doped birnessite are changed, the method is used in sewage treatment to change an ammonia nitrogen oxidation path, an 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 react with ammonium ions in a centering way to realize conversion of ammonia nitrogen into nitrogen, and no nitrate nitrogen and nitrite nitrogen are accumulated in the whole process, so that the method is environment-friendly and free of secondary pollution.
Modified iron doped birnessite is used for treating sewage:
1) Oxygen generated by hydrogen peroxide is adsorbed on 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 charge is carried 2 - Is dissociated into O - The specific process is as follows:
O 2 (dissolved oxygen) →O 2 (oxygen adsorption) (adsorption Process)
O 2 (oxygen adsorption) +e - →O 2 - (Electron transfer Process)
O 2 - +e - →2O - (dissociation procedure)
2) Ammonium ions are adsorbed to the surface of the iron-doped birnessite;
3) The ammonium ion adsorbed to the surface of the modified iron-doped birnessite is oxidized and stripped of hydrogen, the content of oxygen adsorption species on the surface of the modified iron-doped birnessite is increased, the number of N which can be captured is increased, the stability of the oxide species is poor, the oxidation degree is low, and the modified product is converted into nitrite from nitrate;
4) The modified iron doped birnessite is reduced to divalent manganese by trivalent manganese and tetravalent manganese in the crystal lattice of the modified iron doped birnessite while oxidizing ammonium ions; the bivalent manganese is oxidized and converted into trivalent manganese and tetravalent manganese under the action of dissolved oxygen, and the modified iron doped birnessite structure is restored;
5) Nitrite newly generated in the water body and unreacted ammonium are subjected to a centering reaction under the catalysis of modified iron-doped birnessite to generate N 2 The system was drained.
2Mn 5+ +(O - /O 2 - /O 2 2- ) Adsorption of nitrogen +NH 4 + →2Mn 2+ +NO 2 - +4H +
2Mn 3+ +(O - /O 2 - /O 2 2- ) Adsorption of nitrogen +NH 4 + →2Mn 2+ +NO 2 - +4H +
NH 4 + +NO 2 - →N 2 +2H 2 O
Example 1
Preparation of modified iron-doped birnessite (a):
900mL of potassium permanganate solution with the concentration of 0.5mol/L is prepared;
preparing 1L of mixed solution containing 0.35mol/L manganese chloride and 0.35mol/L ferrous chloride, and regulating the pH value of the mixed solution to 2 by using 1M hydrochloric acid;
slowly dripping the prepared potassium permanganate solution into the manganese chloride and ferrous chloride mixed solution, continuously stirring for 2 hours after the dripping is finished, sealing a beaker after the dripping is finished, standing for 50 minutes, filtering after the reaction is completed, and washing with deionized water to obtain the iron-doped birnessite.
80g of iron-doped birnessite is weighed, 80mL of 30% hydrogen peroxide is dripped on the surface of the iron-doped birnessite, stirring is continued in the dripping process, after the dripping is finished, sealing is carried out for 2 hours, and washing and filtering are carried out, thus obtaining the modified iron-doped birnessite (I).
The particle size of the obtained modified iron-doped birnessite is 300nm-500nm.
Fig. 2 (a) shows iron-doped birnessite before modification, and (b) shows modified iron-doped birnessite (a).
From the SEM image, the iron doped birnessite (I) has more fold structures, and after being modified by hydrogen peroxide, the fold structures collapse slightly, but still have sparse and fluffy surface structures, so that more adsorption and reaction sites are provided for ammonia nitrogen catalysis.
The modified iron doped birnessite (I) is applied to sewage treatment:
as shown in Table 1, actual sewage of the Beijing Micloud municipal sewage plant is used as experimental water, and initial ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen concentrations of the experimental water are 56mg/L, 0.6mg/L, 1.2mg/L and 58mg/L respectively.
And (3) placing the prepared modified iron-doped birnessite (I) into sewage, stirring and continuously aerating, and sampling and measuring ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen content in the solution at intervals.
As shown in Table 1, ammonia nitrogen and total nitrogen are reduced along with the increase of aeration time, the nitrosamine content is in a trend of increasing firstly and then reducing, and the nitrosamine concentration is basically unchanged in the whole operation process; this phenomenon indicates that ammonia nitrogen is free of NO during oxidation using the catalyst 3 - The produced product is mainly nitrite, the nitrite can react with ammonium in the operation process to generate nitrogen, the operation is carried out for 20 hours, the total nitrogen is reduced to below 1mg/L, and the experiment proves that the catalytic material has high ammonia nitrogen degradation efficiency, no secondary pollution and practical application prospect.
As shown in FIG. 3, the water body of the Beijing green lake municipal sewage treatment plant is used as experimental water, the initial ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen concentrations 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, the continuous aeration is carried out, the ammonia nitrogen and total nitrogen of the produced water are below 1mg/L, and the performance attenuation phenomenon still does not occur in the continuous treatment of 200L wastewater, so that the ammonia nitrogen in the sewage can be continuously and stably treated by using the modified iron-doped birnessite (I), the produced water meets the surface III water requirement, and the modified iron-doped birnessite can be widely applied to the actual wastewater treatment.
Table 1 detection data of modified iron doped sodium manganese (I) Water obtained in example I after actual wastewater from Peking Mitsui municipal wastewater plant
Example two
Preparation of modified iron-doped birnessite (ii):
900mL of potassium permanganate solution with the concentration of 0.5mol/L is prepared;
preparing 1L of mixed solution containing 0.35mol/L manganese chloride and 0.35mol/L ferrous chloride, and regulating the pH value of the mixed solution to 2 by using 1M hydrochloric acid;
slowly dropwise adding the prepared potassium permanganate solution into the manganese chloride and ferrous chloride mixed solution while stirring, continuously stirring for 2 hours after the dropwise adding is finished, sealing a beaker after the dropwise adding is finished, standing for 50 minutes, filtering after the reaction is finished, and washing with deionized water to obtain the iron-doped birnessite.
80g of iron-doped birnessite is weighed, 150mL of 30% hydrogen peroxide is dripped on the surface of the iron-doped birnessite, stirring is continuously carried out in the dripping process, after the dripping is finished, sealing is carried out for 2 hours, and washing and filtering are carried out, thus obtaining the modified iron-doped birnessite (II).
The particle size of the obtained modified iron-doped birnessite is 300nm-500nm.
Application of modified iron doped birnessite (II) in sewage treatment:
as shown in Table 2, actual sewage of the Beijing Micloud municipal sewage plant is used as experimental water, and initial ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen concentrations of the experimental water are 56mg/L, 0.6mg/L, 1.2mg/L and 58mg/L respectively.
And (3) placing the prepared modified iron-doped birnessite (II) into sewage, stirring and continuously aerating, and sampling and measuring ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen content in the solution at intervals.
As shown in Table 2, the ammonia nitrogen and the total nitrogen are reduced along with the increase of the aeration time, the nitrosamine content is in a trend of increasing firstly and then reducing secondly, and the nitrosamine concentration is basically unchanged in the whole operation process; this phenomenon suggests that ammonia nitrogen is free of NO during oxidation using modified iron doped birnessite (II) 3 - The produced product is mainly nitrite, the nitrite can react with ammonium in the operation process to generate nitrogen, the total nitrogen can be reduced to below 1mg/L in operation for 23 hours, 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 along with the degradation efficiency of ammonia nitrogen, 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 Water obtained in example two after actual wastewater from Beijing Micloud municipal wastewater treatment plant
Example III
Preparation of modified iron-doped birnessite (iii):
900mL of potassium permanganate solution with the concentration of 0.5mol/L is prepared;
preparing 1L of mixed solution containing 0.35mol/L manganese chloride and 0.35mol/L ferrous chloride, and regulating the pH value of the mixed solution to 2 by using 1M hydrochloric acid;
slowly dripping the prepared potassium permanganate solution into the manganese chloride and ferrous chloride mixed solution, continuously stirring for 2 hours after dripping, sealing a beaker after dripping, standing for 50min, filtering after the reaction is completed, and washing with deionized water to obtain the iron-doped birnessite.
Weighing 80g of iron-doped birnessite, dripping 200mL of 30% hydrogen peroxide on the surface of the iron-doped birnessite, continuously stirring in the dripping process, sealing for 2h after the dripping is finished, washing, and filtering to obtain modified iron-doped birnessite (III).
The particle size of the obtained modified iron-doped birnessite is 300nm-500nm.
Application of modified iron doped birnessite (III) in sewage treatment:
as shown in Table 3, actual sewage of the Beijing Micloud municipal sewage plant is used as experimental water, and initial ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen concentrations of the experimental water are 56mg/L, 0.6mg/L, 1.2mg/L and 58mg/L respectively.
And placing the prepared modified iron-doped birnessite (III) ore into sewage, stirring and continuously aerating, and sampling and measuring ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and total nitrogen content in the solution at intervals.
As shown in table 3, the ammonia nitrogen and total nitrogen are reduced along with the increase of the aeration time, the nitrosamine content is in a trend of increasing firstly and then reducing, and the nitrosamine concentration is basically unchanged in the whole operation process; this phenomenon indicates that ammonia nitrogen is free of NO during oxidation using the catalyst 3 - The product is mainly nitrite, the nitrite can react with ammonium in the operation process to generate nitrogen, the operation is carried out for 26 hours, the total nitrogen is reduced to below 1mg/L, the ammonia nitrogen degradation efficiency is reduced along with the reduction of the mass ratio of iron doped birnessite to hydrogen peroxide, but no secondary pollution is caused, and the total nitrogen can be reduced to below 1mg/L by using the catalyst, and the catalyst is environment-friendly and has practical application prospect.
Table 3 detection data of modified iron-doped sodium-manganese Water obtained in example III after actual wastewater from Beijing Micloud municipal wastewater treatment plant
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
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, dripping hydrogen peroxide onto the cake-shaped iron-doped birnessite, reacting, washing, and suction filtering to obtain modified iron-doped birnessite; the mass ratio of the iron doped birnessite to the hydrogen peroxide is 1-3:1;
dropwise adding hydrogen peroxide into cake-shaped iron-doped birnessite, stirring, sealing a beaker after the dropwise adding is finished, standing for 20-60min, and performing suction filtration and washing after the standing is finished to obtain modified iron-doped birnessite; 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 dissolution to obtain a manganese chloride and ferrous chloride mixed solution;
hydrochloric acid is adopted to adjust the acidity of the mixed solution of manganese chloride and ferrous chloride, and the pH value of the mixed solution of manganese chloride and ferrous chloride is 2-3;
dropwise adding 0.5-2mol/L potassium permanganate solution into manganese chloride and ferrous chloride mixed solution, wherein potassium permanganate: manganese chloride: the molar ratio of the ferric chloride is 3:2:2; and (3) after stirring and reacting for a certain time, filtering and washing to obtain the iron doped birnessite.
2. The method for modifying iron-doped birnessite according to claim 1, wherein: the mass ratio of the iron doped birnessite to the hydrogen peroxide is 3:1.
3. The method for modifying iron-doped birnessite according to claim 1, wherein: the mass fraction of hydrogen peroxide was 30%.
4. The method for modifying iron-doped birnessite according to claim 1, wherein: the particle size range of the obtained modified iron-doped birnessite is 300nm-900nm.
5. The method for modifying iron-doped birnessite according to claim 4, wherein: adding hydrogen peroxide into cake-shaped iron-doped birnessite dropwise, stirring, sealing the beaker after the dripping is finished, and standing for 50min.
6. A modified iron-doped birnessite obtained based on the iron-doped birnessite modification method of any one of claims 1-5.
7. Use of a modified iron-doped birnessite according to claim 6.
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