CN110818059A - Non-photoelectric response composite deammoniation material, preparation method and application thereof in sewage deammoniation - Google Patents
Non-photoelectric response composite deammoniation material, preparation method and application thereof in sewage deammoniation Download PDFInfo
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- CN110818059A CN110818059A CN201911203564.4A CN201911203564A CN110818059A CN 110818059 A CN110818059 A CN 110818059A CN 201911203564 A CN201911203564 A CN 201911203564A CN 110818059 A CN110818059 A CN 110818059A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/22—O2
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention provides a non-photoelectric response composite deammoniation material, a preparation method and application thereof in sewage deammoniation, belonging to the technical field of sewage deammoniation materials3N4MnO as main active component of catalyst2And a cocatalyst Bi2O3/WO3A complex; adsorbing dissolved oxygen in water to the surface of the catalyst to generate intermediate products O and OH, and reacting NH with activated O and OH4 +By oxidation to N2. The method can efficiently convert ammonia nitrogen into nitrogen only by utilizing dissolved oxygen in water, is convenient to operate, has low energy consumption and saves cost; the ammonia nitrogen in the wastewater can be effectively degraded, the ammonia nitrogen in the produced water is ensured to be less than 1mg/L, and the requirements of earth surface III water are met; in the process of treating low-concentration ammonia nitrogen wastewater, the ammonia nitrogen can be oxidized and degraded, and the generation of nitrate nitrogen and nitrite nitrogen can be effectively avoided, so that the ammonia can be treatedThe nitrogen is oxidized into nitrogen and discharged, so that secondary pollution is avoided; the composite catalytic material can always keep the stability of water production in the long-term operation process, and the performance attenuation can not occur.
Description
Technical Field
The invention relates to the technical field of sewage deammoniation materials, in particular to a non-photoelectric response composite deammoniation material for oxidizing and degrading ammonia nitrogen into nitrogen by utilizing dissolved oxygen in a water body, a preparation method and application thereof in sewage deammoniation.
Background
Ammonia nitrogen is used as an important pollution source in water, and the exceeding of the content of ammonia nitrogen not only brings great harm to human health, but also has great influence on the ecological environment. Aiming at the ammonia nitrogen treatment of municipal water, besides the traditional biological ammonia nitrogen treatment technology, the method mainly comprises an ion exchange technology and an advanced oxidation technology.
Although the ion exchange technology can selectively remove ammonia nitrogen, when the ion exchange material is saturated in adsorption, the ion exchange material needs to be regenerated, and the adsorption capacity of the adsorption material on the market is very low, so that the ion exchange material needs to be frequently regenerated in the process of ammonium removal, and the secondary treatment cost of high-concentration ammonia nitrogen in the regeneration liquid is very high, thereby limiting the engineering application of the ion exchange material.
The advanced oxidation technology is a water treatment technology newly developed in the field of environment in recent years, and is widely researched due to the advantages of strong oxidation capacity, high reaction speed, convenience in use, small secondary pollution and the like, and the process mainly generates hydroxyl radicals (OH) with strong oxidation capacity through the effects of electricity, sound, light irradiation and the like to oxidize and degrade ammonia nitrogen. Depending on the manner of generating radicals and the reaction conditions, photochemical catalytic oxidation, electrochemical oxidation, and the like can be used.
The photochemical oxidation degrades ammonia nitrogen in the solution, long-time light source irradiation is needed, energy loss is large, and in most cases, a catalyst needs to be doped, so that the treatment cost is high, and the application of the catalyst is limited. The electrochemical oxidation method mainly relies on highly oxidizing substances generated in the electrolytic process, such as chlorine, hypochlorous acid, H2O2And the like, oxidizing and degrading ammonia nitrogen, wherein the ammonia nitrogen in the solution is degraded by adopting an electrochemical oxidation method, and extra chloride ions and H are required to be added into the water body2O2The degradation efficiency of the catalyst on ammonia nitrogen is improved, the whole reaction needs to be maintained by electricity, the cost is high, the energy consumption is high, and the application of the catalyst on engineering is hindered.
Disclosure of Invention
The invention aims to provide non-photoelectric response MnO for effectively degrading ammonia nitrogen in water body by using dissolved oxygen in water without the help of photoelectricity or extra addition of an oxidizing agent2/Bi2O3/WO3/C3N4Composite deammoniation material to solve at least one technical problem in the background art.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a non-photoresponsive composite deammoniation material comprising a catalyst and a support C3N4The catalyst comprises a main active component MnO of the catalyst2And a cocatalyst Bi2O3/WO3A complex; the composite material adsorbs dissolved oxygen in water to the surface of the catalyst to generate intermediate products O and OH, and NH is generated by the activated O and OH4 +By oxidation to N2；
MnO as main active component of catalyst2The catalyst is used for supplementing oxygen vacancy by adsorbing oxidizing gas and ensuring the catalytic activity of the catalyst through the configuration of a mixed-valence octahedral molecular sieve;
cocatalyst Bi2O3/WO3Composite for modifying MnO2By the electronic structure and surface properties of Bi3+Instead of W6+The empty acupuncture points generated at the positions provide activity spaces for lattice oxygen;
carrier C3N4The catalyst has a mesoporous structure and defects, and is used for improving the pore structure of the catalyst and promoting the entry of reactants and the exit of products.
On the other hand, the invention provides a preparation method of a non-photoelectric response composite deammoniation material, which comprises the following process steps: weighing a certain amount of manganese nitrate and bismuth nitrate, dissolving in deionized water, raising the temperature, dropwise adding an alkali solution while stirring, filtering, drying to obtain solid powder, uniformly mixing the solid powder with ammonium tungstate powder and urea in an ethanol solution, drying, placing in a muffle furnace, calcining under the protection of nitrogen, and grinding into powder to obtain MnO (manganese dioxide)2/Bi2O3/WO3/C3N4The composite deammoniation material MO.
Preferably, the preparation method further comprises:
MnO2/Bi2O3/WO3/C3N4forming a composite deammoniation material: dissolving PVC in an organic solvent DMAc under the condition of stirring to form a viscous solution, adding the composite deammoniation material into the viscous solution, continuously stirring until the mixture is uniformly mixed to obtain a mixed solution, and extruding the mixed solution into a deionized water solution through an injector at a certain speed by utilizing a phase inversion principle to form catalyst particles.
Preferably, the ratio of Mn in manganese nitrate and bismuth nitrate: the molar ratio of Bi is 10: 3.
Preferably, the alkali solution is NaOH solution, and the molar ratio of the hydroxide ions of the dropwise added alkali solution to the mixed ions of manganese ions and bismuth ions is 8: 1.
Preferably, the mass ratio of the solid powder to the ammonium tungstate powder and the urea is 10:1: 5.
Preferably, the mass ratio of the composite deammoniation material to the PVC to the DMAc is 85: 15: 160.
preferably, raising the temperature, and raising the temperature to 75 ℃ when dropwise adding the alkali solution while stirring; drying in an oven at 80 deg.C for 10 hr; during calcination, the muffle furnace is calcined for 2 hours at the temperature rise rate of 5 ℃/min and the temperature of 550 ℃.
In a third aspect, the invention also provides an application of the non-photoelectric response composite deammoniation material in sewage deammoniation.
Preferably, the application comprises: wastewater to be treated is collected by a water collecting tank, sewage in the water collecting tank enters a filter column through a booster pump, and the filter column is filled with formed composite deammoniation material particles; the bottom end of the filter column is provided with an aeration port, and air enters the filter column from the aeration port through an aeration pump to provide dissolved oxygen for a reaction system; the wastewater to be treated contacts with the composite deammoniation material particles in the filter column, the composite deammoniation material adsorbs dissolved oxygen in water to the surface of the catalyst particles to generate intermediate products O and OH, and the activated O and OH react with NH4 +By oxidation to N2(ii) a The water body treated by the filter column flows out of the water production pipe through the water production port.
The invention has the beneficial effects that: MnO2/Bi2O3/WO3/C3N4The composite deammoniation material utilizes the high-efficiency catalytic oxidation capacity of the composite deammoniation material, does not need any external means such as photoelectricity and the like, does not need to add chemical agents, can efficiently convert ammonia nitrogen into nitrogen only by utilizing dissolved oxygen in water, is convenient to operate, has low energy consumption and saves cost. Through the molding of the composite deammoniation material and the treatment of municipal sewage in a column-passing mode, the ammonia nitrogen in the wastewater can be effectively degraded to ensure that the ammonia nitrogen in the produced water<1mg/L, meeting the requirement of III-class water on the earth surface. MnO2/Bi2O3/WO3/C3N4The composite deammoniation material can adsorb and enrich NH in water body in use4 +Meanwhile, the ammonia nitrogen and the nitrite nitrogen can be effectively prevented from being generated in the oxidation process, so that the ammonia nitrogen is oxidized into nitrogen to be discharged, and secondary pollution is avoided. The composite catalytic material can always keep the stability of water production in the long-term operation process, and the performance attenuation can not occur.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows a non-photoresponsive MnO in accordance with an embodiment of the present invention2/Bi2O3/WO3/C3N4The scanning schematic diagram of the composite deammoniation material by a 500-fold electron microscope.
FIG. 2 shows a non-photoresponsive MnO in accordance with an embodiment of the present invention2/Bi2O3/WO3/C3N4The scanning schematic diagram of the composite deammoniation material by a 10-kilo-fold electron microscope.
FIG. 3 shows a non-photoresponsive MnO in accordance with an embodiment of the present invention2/Bi2O3/WO3/C3N4The composite deammoniation material is a schematic diagram of the deammoniation principle.
FIG. 4 illustrates the use of MnO in embodiments of the present invention2/Bi2O3/WO3/C3N4A flow chart of a device for wastewater deamination by using the composite deamination material.
FIG. 5 illustrates the use of MnO in an embodiment of the present invention2/Bi2O3/WO3/C3N4Schematic diagram of the change of ammonia nitrogen and total nitrogen content before and after the treatment of the composite deammoniation material along with the amount of wastewater to be treated.
FIG. 6 illustrates the use of MnO in embodiments of the present invention2/Bi2O3/WO3/C3N4Schematic diagram of the change of ammonia nitrogen nitrate nitrogen concentration in inlet water and produced water after 150L of wastewater is treated by the composite deammoniation material.
Wherein: 1-sewage water collecting tank; 2, a booster pump; 3-a liquid flow meter; 4-filtering the column; 5-a sampling port; 6-an air flow meter; 7-an aeration pump; 8-a valve; 9-water production pipe; 10-composite deammoniated material particles; 11-gas.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below by way of the drawings are illustrative only and are not to be construed as limiting the invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
In the description of this patent, it is to be understood that the terms "center," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientations and positional relationships indicated in the drawings for the convenience of describing the patent and for the simplicity of description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the patent.
In the description of this patent, it is noted that unless otherwise specifically stated or limited, the terms "mounted," "connected," and "disposed" are to be construed broadly and can include, for example, fixedly connected, disposed, detachably connected, disposed, or integrally connected and disposed. The specific meaning of the above terms in this patent may be understood by those of ordinary skill in the art as appropriate.
For the purpose of facilitating an understanding of the present invention, the present invention will be further explained by way of specific embodiments with reference to the accompanying drawings, which are not intended to limit the present invention.
It should be understood by those skilled in the art that the drawings are merely schematic representations of embodiments and that the elements shown in the drawings are not necessarily required to practice the invention.
Example 1
As shown in figures 1 and 2, the embodiment 1 of the invention provides a non-photoresponse composite deammoniation material, which comprises a catalyst and a carrier C3N4The catalyst comprises a main active component MnO of the catalyst2And a cocatalyst Bi2O3/WO3A complex; the composite material adsorbs dissolved oxygen in water to the surface of the catalyst to generate intermediate products O and OH, and NH is generated by the activated O and OH4 +By oxidation to N2. MnO as main active component of catalyst2The catalyst is used for supplementing oxygen vacancy by adsorbing oxidizing gas and ensuring the catalytic activity of the catalyst through the mixed-valence octahedral molecular sieve configuration. Cocatalyst Bi2O3/WO3Composite for modifying MnO2By the electronic structure and surface properties of Bi3+Instead of W6+The empty acupuncture points generated at the positions provide activity spaces for lattice oxygen. Carrier C3N4The catalyst has a mesoporous structure and defects, and is used for improving the pore structure of the catalyst and promoting the entry of reactants and the exit of products.
In summary, the non-photoresponsive composite deammoniating material, package, described in example 1 of the present inventionContains four functional materials. First, MnO as the main active component of the catalyst2。MnO2Belonging to the n-type semiconductor, the composition of which does not completely conform to the stoichiometry, always has a small amount of oxygen deficiency, and strictly represents MnOy(1.5<y<2) Oxygen vacancies are replenished by adsorption of oxygen or other oxidizing gases and manganese dioxide has mixed valence (Mn) in its structure3+And Mn4+) The octahedral molecular sieve configuration enables the manganese dioxide to have certain activity in catalytic reaction.
Secondly, use Bi2O3/WO3The compound acts as a cocatalyst. Bi2O3/WO3Modifying MnO as an electron adjuvant in a system2Electronic structure and surface properties of, WO3Has W6+To W5+Thereby the catalyst has good electron transfer characteristics and catalytic oxidation activity. In addition, WO3And Bi2O3After doping, a small portion of Bi3+Replace W6+The position generates empty acupuncture points, provides a larger movement space for lattice oxygen, and improves the movement and transfer capacity of the lattice oxygen in the catalyst, thereby greatly improving the catalytic oxidation capacity of the catalyst. WO3And Bi2O3Can provide more oxygen to Mn, contributing to higher-valence MnO2Thereby promoting the oxidation reaction and improving the removal rate of the catalyst to ammonia nitrogen.
Finally, using C3N4As a carrier. C3N4The catalyst has large specific surface area, a mesoporous structure and defects, and can improve the pore structure of the catalyst, promote the entering of reactants and the leaving of products, thereby improving the efficiency and improving the capture capacity of the catalytic material to the dissolved oxygen in water. Further, C having a large specific surface area3N4The carrier is favorable for dispersing the active components, so that more reactive active sites are exposed on the surface, further the oxidation reaction is more favorably carried out, and the using amount of the catalyst is greatly reduced.
The composite catalytic material takes metal oxide as a main body, and the solid surface of the metal oxide isThe surface of the material is easy to be hydroxylated by water adsorption to have negative charges, so that the material has good adsorption effect on positive charged cations. The working principle of the composite material is as follows: firstly, the dissolved oxygen in the water body and a certain amount of water are adsorbed on the surface of a catalyst by utilizing a material to generate intermediate products O and OH with strong oxidizing property, and NH in an adsorbed state is subjected to double actions of O and OH in an activated state4 +By oxidation to N2And (4) discharging.
As shown in fig. 3, the working principle of the composite deammoniation material is as follows: firstly, the material is utilized to react with NH4 +The adsorption performance of the catalyst is that the catalyst is enriched on the surface of a composite material from a water body, simultaneously, dissolved oxygen in the water body is adsorbed on the surface of the catalyst to generate an intermediate product O with strong oxidizing property, and NH in an adsorption state is adsorbed under the action of the O in an activation state4 +Reaction to form N2. Under the condition of high catalytic activity, ammonia nitrogen in water is fully contacted with active components in a column passing mode, so that the effect of stably and efficiently removing the ammonia nitrogen in the water body is achieved. The basic reaction is as follows:
MO+O2＝＝＝＝MO+2O·
6O·+4NH4 +＝＝＝＝2N2↑+6H2O+4H+
example 2
MnO2/Bi2O3/WO3/C3N4The synthesis method of the composite deammoniation material powder comprises the following steps: weighing a certain amount of manganese nitrate and bismuth nitrate, and dissolving the manganese nitrate and the bismuth nitrate in deionized water, wherein the ratio of Mn: the molar ratio of Bi is 10:3, NaOH aqueous solution is dropwise added while stirring at 75 ℃, the molar ratio of hydroxide ions in the alkaline solution to the quantitative mixed ions in the manganese-bismuth mixed aqueous solution is 8:1, the mixture is continuously stirred at 75 ℃ for 2 hours and then filtered, the obtained solid is put into an oven at 80 ℃ for drying for 10 hours, the obtained solid powder is uniformly mixed with ammonium tungstate powder and urea in an ethanol solution according to the mass ratio of 10:1:5, and after drying, the obtained solid powder is uniformly mixed with the ammonium tungstate powder and the urea in the ethanol solutionPlacing the mixture in a muffle furnace, calcining the mixture for 2 hours at the temperature rise rate of 5 ℃/min and the temperature of 550 ℃ under the protection of nitrogen to obtain MnO2/Bi2O3/WO3/C3N4The composite deammoniated material (abbreviated as MO) is ground to a powder for use.
MnO2/Bi2O3/WO3/C3N4Forming a composite deammoniation material: selecting PVC as a macromolecular adhesive, selecting DMAC as an organic solvent, and weighing a catalyst, the PVC and the DMAc according to a certain mass ratio, wherein the mass ratio of the three substances is as follows: PVC: DMAc 85: 15: 160. the method comprises the following specific steps: PVC is dissolved in an organic solvent DMAc under the stirring condition to form a solution with certain viscosity, then a composite deammoniation material is added into the solution and is continuously stirred until the solution is uniformly mixed, and the mixed solution is extruded into a deionized water solution through an injector according to a certain speed by utilizing the phase inversion principle to form catalyst particles.
As shown in figures 1 and 2, the composite deammoniation material prepared by the embodiment 2 of the invention comprises a catalyst and a carrier C3N4The catalyst comprises a main active component MnO of the catalyst2And a cocatalyst Bi2O3/WO3A complex; the composite material adsorbs dissolved oxygen in water to the surface of the catalyst to generate intermediate products O and OH, and NH is generated by the activated O and OH4 +By oxidation to N2. MnO as main active component of catalyst2The catalyst is used for supplementing oxygen vacancy by adsorbing oxidizing gas and ensuring the catalytic activity of the catalyst through the mixed-valence octahedral molecular sieve configuration. Cocatalyst Bi2O3/WO3Composite for modifying MnO2By the electronic structure and surface properties of Bi3+Instead of W6+The empty acupuncture points generated at the positions provide activity spaces for lattice oxygen. Carrier C3N4The catalyst has a mesoporous structure and defects, and is used for improving the pore structure of the catalyst and promoting the entry of reactants and the exit of products.
Example 3
As shown in fig. 4, in embodiment 3 of the present invention, wastewater to be treated is collected by a water collection tank 1, sewage in the water collection tank enters a filtration column 4 (i.e., a composite deammoniation material adsorption column) through a booster pump 2, the filtration column is filled with a molded composite deammoniation material (composite deammoniation material particles 10), a water inlet pipeline is provided with a liquid flow meter 3 to quantitatively control inlet water, and the water stays in the filtration column for 30-40min under hydraulic power, so that the water to be treated is fully contacted with the composite deammoniation material. The filter column is made of organic glass, the inner diameter is 0.025m, the height is 0.5m, and five sampling ports 5 are arranged at the lower end of the filter column and used for monitoring water body components at different positions. The bottom is the aeration mouth, makes the air get into in the post through aeration pump 7, for reaction system provides abundant dissolved oxygen, carries out quantitative control to the air with air flowmeter 6 simultaneously to because the aeration is full of gaseous 11, after the processing is accomplished, open valve 8, the water after the filter column processing is through producing the mouth of a river by producing water pipe 9 and flow out. According to the process flow, ammonia nitrogen in the water body can be effectively oxidized and degraded, so that the ammonia nitrogen in the produced water is stabilized below 1mg/L, and the total nitrogen in the produced water is less than 1mg/L, thereby meeting the requirements of surface III water.
Composite deaminizing material deaminizing performance detection experiment I
Taking an actual water sample back for a certain municipal sewage treatment plant by using inflow water, enabling 100L of municipal sewage to enter a 1L-volume catalyst adsorption column through a peristaltic pump at the inflow speed of 5mL/min, enabling the municipal sewage to stay for 40min by waterpower, enabling the column packing to share 300g of composite deammoniation material powder, wherein the effective component is 255g, opening an air inlet valve for aeration, enabling the air flow to be 20mL/min, and sampling at intervals to monitor the changes of ammonia nitrogen and total nitrogen of inflow water and outflow water. The test result is shown in figure 5, the inflow ammonia nitrogen and the total nitrogen are respectively about 45mg/L and 47mg/L, after the adsorption column treats 100L of sewage, the ammonia nitrogen and the total nitrogen are respectively 0.6mg/L and 1.2mg/L, the ammonia nitrogen in the produced water is always maintained below 1mg/L in the operation process, and the total nitrogen in the produced water is less than 1mg/L, so that the requirements of surface III-class water are met, and the operation is stable. And the total nitrogen is reduced to 1.2mg/L from 47mg/L, which shows that ammonia nitrogen is mainly converted into nitrogen gas instead of nitrate nitrogen in the catalysis process, and no secondary pollution is caused.
Composite deaminizing material deaminizing performance detection experiment II
And (2) allowing 150L of municipal sewage to enter a catalyst adsorption column with the volume of 1L through a peristaltic pump at the water inlet speed of 8mL/min, allowing the municipal sewage to stay for 30min by waterpower, filling the column with 300g of composite deammoniation material powder, wherein the effective component is 255g, opening an air inlet valve for aeration, and allowing the air flow to be 40 mL/min. As shown in figure 6, after 150L of sewage is treated by the adsorption column, the inflow ammonia nitrogen and the total nitrogen are respectively reduced to 0.7mg/L and 1.3mg/L from 53mg/L and 55mg/L, the produced water ammonia nitrogen is always maintained below 1mg/L in the operation process, the fluctuation is small, no nitrate nitrogen is increased in the produced water, the total nitrogen of the produced water is less than 1mg/L, the produced water ammonia nitrogen meets the requirement of III-class water on the ground surface, and the large-scale practical application can be carried out.
In summary, the non-photoelectric-response composite deammoniation material provided by the embodiment of the present invention is a non-photoelectric-response material, and the material is used to adsorb dissolved oxygen in a water body and a certain amount of water onto the surface of a catalyst to generate intermediate products O and OH with strong oxidizing property, and adsorb enriched NH on the surface of the material under the dual action of the activated O and OH4 +By oxidation to N2And (4) discharging. The problems that the ammonia nitrogen waste liquid needs to be regenerated frequently and the regeneration cost is high when the ammonia nitrogen waste liquid is treated by adopting an ion exchange method are solved; the problems of increased energy consumption cost, secondary pollution and the like caused by the fact that an advanced oxidation technology needs auxiliary means such as photoelectricity to degrade ammonia nitrogen or needs an additional oxidant to be added are solved; solves the problems of limited catalytic ability of the catalyst and low ammonia nitrogen conversion efficiency in the catalytic oxidation method. The material comprises four functional materials.
Using MnO2As the main active component of the catalyst. MnO2Belonging to n-type semiconductors, the composition of which is not entirely in accordance with chemistryMeasured, always small amount of oxygen deficiency, expressed as MnOy(1.5<y<2) Oxygen vacancies are replenished by adsorption of oxygen or other oxidizing gases, and manganese dioxide has a mixed valence (Mn) in its structure3+And Mn4+) The octahedral molecular sieve configuration enables the manganese dioxide to have certain activity in catalytic reaction.
Use of Bi2O3/WO3The compound acts as a cocatalyst. Bi2O3/WO3Modifying MnO as an electron adjuvant in a system2Electronic structure and surface properties of, WO3Has W6+To W5+Thereby the catalyst has good electron transfer characteristics and catalytic oxidation activity. WO3And Bi2O3After doping, a small portion of Bi3+Replace W6+The position generates empty acupuncture points, provides a larger movement space for lattice oxygen, and improves the movement and transfer capacity of the lattice oxygen in the catalyst, thereby greatly improving the catalytic oxidation capacity of the catalyst. In addition, WO3And Bi2O3Can provide more oxygen to Mn, contributing to higher-valence MnO2Thereby promoting the oxidation reaction and improving the removal rate of the catalyst to ammonia nitrogen.
Use of C3N4As a carrier. C3N4The catalyst has large specific surface area, a mesoporous structure and defects, and can improve the pore structure of the catalyst, promote the entering of reactants and the leaving of products, thereby improving the efficiency and improving the capture capacity of the catalytic material to the dissolved oxygen in water. Further, C having a large specific surface area3N4The carrier is favorable for dispersing the active components, so that more reactive active sites are exposed on the surface, further the oxidation reaction is more favorably carried out, and the using amount of the catalyst is greatly reduced. In addition, the composite catalytic material takes the metal oxide as a main body, and the solid surface of the metal oxide and the surface of the metal oxide are easy to hydroxylate due to water adsorption so as to have negative charges, so that the composite catalytic material has good adsorption effect on positive charged cations.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A non-photoelectric response composite deammoniation material is characterized in that:
the composite deammoniation material comprises a catalyst and a carrier C3N4The catalyst comprises a main active component MnO of the catalyst2And a cocatalyst Bi2O3/WO3A complex; the composite material absorbs dissolved oxygen in water body to the surface of the catalyst to generate intermediate products O and OH, and NH is generated by the activated O and OH4 +By oxidation to N2；
MnO as main active component of catalyst2The catalyst is used for supplementing oxygen vacancy by adsorbing oxidizing gas and ensuring the catalytic activity of the catalyst through the configuration of a mixed-valence octahedral molecular sieve;
cocatalyst Bi2O3/WO3Composite for modifying MnO2By the electronic structure and surface properties of Bi3+Instead of W6+The empty acupuncture points generated at the positions provide activity spaces for lattice oxygen;
carrier C3N4The catalyst has a mesoporous structure and defects, and is used for improving the pore structure of the catalyst and promoting the entry of reactants and the exit of products.
2. A preparation method of a non-photoelectric response composite deammoniation material is characterized by comprising the following process steps:
weighing a certain amount of manganese nitrate and bismuth nitrate, dissolving in deionized water, raising the temperature, dropwise adding an alkali solution while stirring, filtering, drying to obtain solid powder, uniformly mixing the solid powder with ammonium tungstate powder and urea in an ethanol solution, drying, placing in a muffle furnace, calcining under the protection of nitrogen, and grinding into powder to obtain MnO (manganese dioxide)2/Bi2O3/WO3/C3N4The composite deammoniation material MO.
3. The method for preparing the non-photoresponsive composite deammoniated material according to claim 2, further comprising:
MnO2/Bi2O3/WO3/C3N4forming a composite deammoniation material: dissolving PVC in an organic solvent DMAc under the condition of stirring to form a viscous solution, adding the composite deammoniation material into the viscous solution, continuously stirring until the mixture is uniformly mixed to obtain a mixed solution, and extruding the mixed solution into a deionized water solution through an injector at a certain speed by utilizing a phase inversion principle to form composite deammoniation material particles.
4. The method for preparing the non-photoresponse composite deammoniation material according to claim 3, characterized in that: mn in manganese nitrate and bismuth nitrate: the molar ratio of Bi is 10: 3.
5. The method for preparing the non-photoresponse composite deammoniation material according to claim 4, characterized in that: the alkaline solution is NaOH solution, and the molar ratio of the hydroxyl ions of the dropwise added alkaline solution to the mixed ions of manganese ions and bismuth ions is 8: 1.
6. The method for preparing the non-photoresponse composite deammoniation material according to claim 5, characterized in that: the mass ratio of the solid powder to the ammonium tungstate powder to the urea is 10:1: 5.
7. The method for preparing the non-photoresponse composite deammoniation material according to claim 6, characterized in that: the mass ratio of the composite deammoniation material to the PVC to the DMAc is 85: 15: 160.
8. the method for preparing a non-photoresponsive composite deammoniated material according to any one of claims 2 to 6, characterized in that: raising the temperature, and raising the temperature to 75 ℃ when dropwise adding the alkali solution while stirring; drying in an oven at 80 deg.C for 10 hr; during calcination, the muffle furnace is calcined for 2 hours at the temperature rise rate of 5 ℃/min and the temperature of 550 ℃.
9. Use of a non-photoresponsive composite deaminating material according to any of claims 1 to 8 for sewage deamination.
10. The use of the non-photoresponsive composite deaminating material of claim 9 for sewage deamination, wherein: wastewater to be treated is collected by a water collecting tank, sewage in the water collecting tank enters a filter column through a booster pump, and the filter column is filled with formed composite deammoniation material particles; the bottom end of the filter column is provided with an aeration port, and air enters the filter column from the aeration port through an aeration pump to provide dissolved oxygen for a reaction system; the wastewater to be treated contacts with catalyst particles in the filter column, the composite deammoniation material adsorbs dissolved oxygen in water to the surfaces of the catalyst particles to generate intermediate products O and OH, and the activated O and OH are used for reacting NH4 +By oxidation to N2(ii) a The water body treated by the filter column flows out of the water production pipe through the water production port.
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