CN114229985A - Novel method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride - Google Patents

Novel method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride Download PDF

Info

Publication number
CN114229985A
CN114229985A CN202111533689.0A CN202111533689A CN114229985A CN 114229985 A CN114229985 A CN 114229985A CN 202111533689 A CN202111533689 A CN 202111533689A CN 114229985 A CN114229985 A CN 114229985A
Authority
CN
China
Prior art keywords
ammonia nitrogen
magnesium
catalytic oxidation
oxyfluoride
wastewater
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111533689.0A
Other languages
Chinese (zh)
Other versions
CN114229985B (en
Inventor
王刚
张振华
李争光
李志鹏
敖志锋
王子龙
石芙蓉
黄路
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Nonferrous Chenzhou Fluorde Chemical Co ltd
Original Assignee
Hunan Nonferrous Chenzhou Fluorde Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Nonferrous Chenzhou Fluorde Chemical Co ltd filed Critical Hunan Nonferrous Chenzhou Fluorde Chemical Co ltd
Priority to CN202111533689.0A priority Critical patent/CN114229985B/en
Publication of CN114229985A publication Critical patent/CN114229985A/en
Application granted granted Critical
Publication of CN114229985B publication Critical patent/CN114229985B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • 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
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • 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

Abstract

The invention provides a method for removing ammonia nitrogen by catalytic oxidation of novel magnesium-based oxyfluoride, which comprises the following steps: treating ammonia nitrogen wastewater by adopting novel magnesium-based oxyfluoride and oxidant for catalytic oxidation; the preparation method of the novel magnesium-based oxyfluoride comprises the following steps: dissolving magnesium chloride and doped metal element salt in water to adjust the pH value to obtain a mixture; mixing the mixture with silica gel and granulating to obtain granules; fluorinating the particles to obtain the novel magnesium-based oxyfluoride compound. The method provided by the invention has the advantages of high ammonia nitrogen removal efficiency, simple flow and no secondary pollution, and the method adopts the magnesium oxyfluoride-based catalyst with better performance for catalysis, does not need to use ozone, adopts conventional hydrogen peroxide, sodium hypochlorite and air, greatly shortens the time for oxidizing and decomposing ammonia nitrogen, and only needs about 20s of contact time, namely the contact timeCan reach NH4+The conversion rate of-N reaches more than 60 percent, and almost no ammonia nitrogen decomposition products exist

Description

Novel method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a novel method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride.
Background
Ammonia nitrogen and the like are common pollutants of water body pollution, and the presence of the ammonia nitrogen can consume a large amount of oxygen in water, so that water body eutrophication is caused, algae plants are propagated in large quantities, and fishes die in large quantities due to oxygen deficiency. In addition, the increase of the ammonia nitrogen concentration increases the chlorine dosage in the disinfection treatment of the drinking water, thereby not only increasing the water treatment cost, but also possibly causing the sharp increase of disinfection byproducts and harming the safety of the drinking water. The ammonia nitrogen concentration in the wastewater is often very high, and the discharge requirement cannot be met by directly adopting biochemical treatment, so an efficient and safe method is needed for treating the ammonia nitrogen substances in the wastewater.
With the rapid development of chemical fertilizer, petrochemical industry and other industries, the generated high ammonia nitrogen wastewater also becomes one of the industry development restriction factors. Therefore, the economic and effective control of high concentration pollution is also an important subject of current research by environmental protection workers, and is highly regarded by the industry. The general formation of ammonia nitrogen wastewater is caused by the coexistence of ammonia water and inorganic ammonia, the main source of ammonia nitrogen in wastewater with pH above neutral is the combined action of inorganic ammonia and ammonia water, and the ammonia nitrogen in wastewater under acidic condition is mainly caused by inorganic ammonia.
The existing methods for treating ammonia nitrogen wastewater mainly comprise an ion exchange method, a breakpoint chlorination method and a chemical precipitation method. The ion exchange method of ammonia nitrogen is to utilize positive ions in an ion exchanger and NH in wastewater4+The method for removing ammonia nitrogen in water by ion exchange has simple and convenient process and convenient operation, does not need to add other medicaments, and can adjust the temperatureThe adaptability is strong, and the method can be widely applied to the treatment of ammonia nitrogen wastewater with low concentration and less impurities; however, the problems of the decrease of the exchange capacity and the deterioration of the treatment effect after the regeneration of the exchanger are often caused, and the ion exchange method is prevented from being practically applied because the regenerated solution of the exchanger needs to be intensively treated. The breakpoint chlorination method has the advantages of simple and convenient operation, reliable effect, no influence of water temperature, no need of additional facilities and the like, but carcinogenic by-products DBPs (such as trihalomethane THMs and the like) can be generated in the chlorination process of ammonia nitrogen wastewater containing organic matters, and the method is harmful to the environment and human bodies. The chemical precipitation method has simple process, particularly has high treatment efficiency aiming at high-concentration ammonia nitrogen wastewater, and the precipitate magnesium ammonium phosphate can be further processed into compound fertilizer; however, the precipitation method needs a large amount of added chemicals, the price of the phosphorus salt and the magnesium salt is high, and the reaction process needs stirring and consumes electric energy.
A catalytic wet oxidation (CWAO) method for treating waste water features that under a certain temp and pressure, the organic substance and ammonia nitrogen in sewage are oxidized by oxygen or air to CO under the catalytic action of catalyst2And N2And the like, without considering secondary treatment. According to the literature report, the construction and operation cost of the catalytic wet oxidation method is only about 60% of that of the conventional method (related to the process and to be tested), and the method can effectively treat ammonia nitrogen wastewater with different concentrations, especially low-concentration or toxic ammonia nitrogen wastewater, so that the catalytic wet oxidation method has more competitive advantages in economy and technology compared with the biological method. The core of the technology for treating ammonia nitrogen wastewater by catalytic wet oxidation is a proper catalyst, and an excellent catalyst has enough high but proper ammonia nitrogen catalytic conversion activity, so that ammonia nitrogen in wastewater can be effectively and selectively oxidized into nitrogen instead of nitrogen oxide. However, the more effective catalysts reported in the prior literature have high noble metal content (more than 3 wt%), and have harsh working conditions, requiring high temperature and high pressure. Research and development of low-temperature efficient and low-price catalyst, quicken the industrial application step of treating ammonia nitrogen wastewater by catalytic wet oxidation technology, effectively solve the pollution problem of water resources in China, and have the advantages ofObvious social development significance.
Disclosure of Invention
In view of the above, the invention aims to provide a novel method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride, and the method provided by the invention can better treat ammonia nitrogen wastewater with medium and low concentration.
The invention provides a method for removing ammonia nitrogen by catalytic oxidation of novel magnesium-based oxyfluoride, which comprises the following steps:
treating ammonia nitrogen wastewater by adopting novel magnesium-based oxyfluoride and oxidant for catalytic oxidation;
the preparation method of the novel magnesium-based oxyfluoride comprises the following steps:
dissolving magnesium chloride and doped metal element salt in water to adjust the pH value to obtain a mixture;
mixing the mixture with silica gel and granulating to obtain granules;
fluorinating the particles to obtain the novel magnesium-based oxyfluoride compound.
Preferably, the pH value is 9-11.
Preferably, the gas used in the fluorination process comprises:
N2and HF.
Preferably, the oxidant is selected from one or more of hydrogen peroxide, sodium hypochlorite, oxygen and air.
Preferably, the method for removing ammonia nitrogen by catalytic oxidation of the novel magnesium-based oxyfluoride comprises the following steps:
the novel magnesium-based oxyfluoride is filled in a fixed bed reactor, an oxidant and ammonia nitrogen wastewater are mixed, and the obtained mixed solution is subjected to catalytic oxidation treatment on the ammonia nitrogen wastewater through the fixed bed reactor.
Preferably, the amount of the novel magnesium-based oxyfluoride is 15-25 g.
Preferably, the diameter of the fixed bed reactor is 0.8-1.2 inches; the length of the fixed bed reactor is 55-65 cm.
Preferably, the flow rate of the mixed solution passing through the fixed bed reactor is 80-120 ml/min.
Preferably, the method for removing ammonia nitrogen by catalytic oxidation of the novel magnesium-based oxyfluoride comprises the following steps:
suspending the novel magnesium-based oxyfluoride in ammonia nitrogen wastewater, mixing an oxidant and the ammonia nitrogen wastewater, and stirring to obtain a mixed solution for carrying out catalytic oxidation treatment on the ammonia nitrogen wastewater.
The ammonia nitrogen wastewater treatment method provided by the invention has the advantages of high ammonia nitrogen removal efficiency, simple process, no secondary pollution and the like compared with the conventional aluminum oxide (Al)2O3) The invention adopts magnesium oxyfluoride base catalyst with better performance to catalyze ozone, does not need ozone, adopts conventional hydrogen peroxide, sodium hypochlorite and air, greatly shortens the time for oxidizing and decomposing ammonia nitrogen, and can reach NH within about 20s of contact time4+The conversion rate of-N reaches more than 60 percent, and almost NO NO is contained in the ammonia nitrogen decomposition products3 -。
Drawings
FIG. 1 is a process flow diagram of the ammonia nitrogen wastewater treatment method in the embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for removing ammonia nitrogen by catalytic oxidation of novel magnesium-based oxyfluoride, which comprises the following steps:
the ammonia nitrogen wastewater is treated by adopting novel magnesium-based oxyfluoride and oxidant for catalytic oxidation.
In the present invention, the preparation method of the novel magnesium-based oxyfluoride comprises:
dissolving magnesium chloride and doped metal element salt in water to adjust the pH value to obtain a mixture;
mixing the mixture with silica gel and granulating to obtain granules;
fluorinating the particles to obtain the novel magnesium-based oxyfluoride compound.
In the present invention, the doped metal element in the doped metal element salt is preferably selected from transition metal elements, and more preferably selected from one or more of chromium, zinc, lanthanum, iron, vanadium, zirconium, nickel, copper, cobalt and lanthanum.
In the present invention, the doped metal element salt is preferably one or more selected from a chloride salt and a nitrate salt of a doped metal element.
In the present invention, the water is preferably pure water.
In the invention, the dosage proportion of the magnesium chloride, the doped metal element salt and the water is preferably (80-120) g: (10-30) g: 1L, more preferably (90-110) g: (15-25) g: 1L, most preferably (95-105) g: (18-22) g: 1L of the compound.
In the invention, ammonia water is preferably adopted in the process of adjusting the pH value; the pH value is preferably 9-11, and more preferably 10.
In the present invention, the mixing is preferably performed under stirring; the mixing time is preferably 20-40 min, more preferably 25-35 min, and most preferably 30 min.
In the present invention, it is preferable that the mixture further comprises:
and filtering the obtained product to obtain the mixture of magnesium oxide and doped metal elements, and precipitating powder.
In the present invention, the mass ratio of the silica gel to the magnesium chloride is preferably 1: (2-100), more preferably 1: (10 to 95), more preferably 1: (30-90), more preferably 1: (50-80), most preferably 1: (60-70).
In the invention, the particle size of the silica gel is preferably 350-450 meshes, more preferably 380-420 meshes, and most preferably 400 meshes.
In the invention, the granulation is preferably carried out by adopting a granulator; the shape of the pellets is preferably cylindrical; the diameter of the cylinder is preferably 1-5 mm, more preferably 2-4 mm, and most preferably 3 mm; the height of the cylinder is preferably 1-10 mm, more preferably 2-8 mm, more preferably 3-6 mm, and most preferably 4-5 mm.
In the present invention, the particles obtained preferably further comprise, before fluorination:
and drying the particles and then cooling.
In the invention, the drying temperature is preferably 280-320 ℃, more preferably 290-310 ℃, and most preferably 300 ℃; the drying is preferably carried out by introducing nitrogen; the drying time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and most preferably 8 hours.
In the invention, the temperature of the temperature reduction is preferably 130-170 ℃, more preferably 140-160 ℃, and most preferably 150 ℃.
In the present invention, the gas used in the fluorination process preferably comprises:
N2and HF.
In the present invention, the fluorination method preferably comprises:
sequentially carrying out primary fluorination, secondary fluorination, tertiary fluorination and quartic fluorination.
In the invention, N is generated in the primary fluorination process2And the preferred volume ratio of HF to HF is (8-12): 1, more preferably (9-11): 1, most preferably 10: 1; the gas flow rate is preferably 80-120 ml/min, more preferably 90-110 ml/min, and most preferably 100 ml/min; the fluorination time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours.
In the present invention, N in the secondary fluorination process2And the preferred volume ratio of HF to HF is (3-7): 1, more preferably (4-6): 1, most preferably 5: 1; the gas flow rate is preferably 80-120 ml/min, more preferably 90-110 ml/min, and most preferably 100 ml/min; the fluorination time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours.
In the present invention, N in the triple fluorination process2And the preferred volume ratio of HF to HF is (2-4): 1, more preferably (2.5 to 3.5): 1, most preferably 3: 1; the gas flow rate is preferably 80-120 ml/min, more preferably 90-110 ml/min, and most preferably 100 ml/min; the fluorination time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours.
In the present invention, N in the four fluorination processes2And the preferred volume ratio of HF to HF is (0.5-1.5): 1, more preferably (0.8 to 1.2): 1, most preferably 1: 1; the gas flow rate is preferably 80-120 ml/min, more preferably 90-110 ml/min, and most preferably 100 ml/min; the fluorination time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours.
According to the novel magnesium-based oxyfluoride, oxygen atoms are replaced by partial fluorine atoms, so that the Lewis acidity of magnesium ions is enhanced, but the catalytic activity of the magnesium oxyfluoride is not strong enough, in order to enhance the catalytic performance of the magnesium oxyfluoride, transition metal elements such as chromium, zinc, lanthanum, iron, vanadium, zirconium, nickel, copper, cobalt and the like are doped in the magnesium oxyfluoride to adjust the Lewis acidity, and meanwhile, the specific surface area of the catalyst is increased by adding a silicon auxiliary agent, so that the catalytic performance of the catalyst is enhanced; the metal doping mode can adopt an adsorption method or a coprecipitation method.
In the invention, the oxidant is preferably one or more selected from hydrogen peroxide, sodium hypochlorite, oxygen and air, and more preferably hydrogen peroxide.
In the present invention, the mass concentration of the hydrogen peroxide is preferably 20 to 30%, more preferably 23 to 27%, and most preferably 25%.
In the invention, the mass content of ammonia nitrogen in the ammonia nitrogen wastewater is preferably 5-30 ppm, more preferably 10-25 ppm, and most preferably 15-20 ppm.
In the invention, preferably, the novel magnesium-based oxyfluoride is filled in a fixed bed reactor, an oxidant and ammonia nitrogen wastewater are mixed, and the obtained mixed solution is subjected to catalytic oxidation treatment on the ammonia nitrogen wastewater through the fixed bed reactor.
In the present invention, the amount of the novel magnesium-based oxyfluoride is preferably 15 to 25g, more preferably 18 to 22g, and most preferably 20 g.
In the invention, the diameter of the fixed bed reactor is preferably 0.8-1.2 inches, and more preferably 1 inch; the length of the fixed bed reactor is preferably 55-65 cm, more preferably 58-62 cm, and most preferably 60 cm.
In the invention, the flow rate of the mixed liquid passing through the fixed bed reactor is preferably 80-120 ml/min, more preferably 90-110 ml/min, and most preferably 100 ml/min.
In the invention, preferably, the novel magnesium-based oxyfluoride is suspended in the ammonia nitrogen wastewater, the oxidant and the ammonia nitrogen wastewater are mixed, and the obtained mixed solution is stirred to perform catalytic oxidation treatment on the ammonia nitrogen wastewater.
In the invention, the proportion of the content of ammonia nitrogen in the novel magnesium-based oxyfluoride, the oxidant and the ammonia nitrogen wastewater is preferably (10-30) g: (0.1-2) g: (10-30) ppm, more preferably (15-25) g: (0.2-1.5) g: (12-25) ppm, most preferably 20 g: (0.5-1) g: (15 to 20) ppm.
In the invention, the temperature of the catalytic oxidation treatment is preferably 70-80 ℃, more preferably 73-77 ℃, and most preferably 75 ℃.
Under the catalysis of novel magnesium-based metal oxyfluoride, oxidizing agents such as hydrogen peroxide, sodium hypochlorite and oxygen oxidize ammonia nitrogen in the wastewater into nitrogen and NH4+The conversion rate of-N reaches more than 60 percent, and the treated wastewater has almost NO NO3 -。
FIG. 1 is a process flow diagram of ammonia nitrogen wastewater treatment in the embodiment of the invention, wherein V-10 is an ammonia nitrogen wastewater tank, V-102 is a hydrogen peroxide, sodium hypochlorite and other oxidant storage tanks, and V-103 is a mixing tank.
The ammonia nitrogen wastewater treatment method provided by the invention has the advantages of high ammonia nitrogen removal efficiency, simple process, no secondary pollution and the like compared with the conventional aluminum oxide (Al)2O3) The invention adopts magnesium oxyfluoride base catalyst with better performance to catalyze ozone, does not need ozone, adopts conventional hydrogen peroxide, sodium hypochlorite and air, greatly shortens the time for oxidizing and decomposing ammonia nitrogen, and can reach NH within about 20s of contact time4+The conversion rate of-N reaches more than 60 percent, and almost NO NO is contained in the ammonia nitrogen decomposition products3 -。
Comparative example 1
20g of alumina is placed in a fixed bed reactor, the alumina is heated to 80 ℃, 1L of wastewater with the ammonia nitrogen mass content of 15ppm and 0.18g of hydrogen peroxide with the mass concentration of 25% are uniformly mixed, the mixed ammonia nitrogen wastewater flows through the fixed bed reactor at the flow rate of 100ml/min by a peristaltic pump for catalytic oxidation, and the discharged ammonia nitrogen wastewater actually measures the ammonia nitrogen mass concentration of 14ppm (tested by adopting a national standard HJ535-2009 method) and hardly converts.
Example 1
Dissolving 94g of magnesium chloride and 15.8g of chromium trichloride in 1L of pure water, slowly adding ammonia water to the solution until the pH value is 10, continuously stirring the solution for reaction for 30min, filtering the solution to obtain a mixture of magnesium oxide and chromium oxide, precipitating the solution to obtain powder, adding 1g of 400-mesh silica gel into the powder, uniformly mixing the powder and the powder, and granulating the powder by using a granulator to obtain magnesium-chromium oxide particles (the diameter is 1.5mm, and the height is 2 mm).
Placing 20g of the obtained magnesium chromium oxide particles in a fixed bed reactor, heating to 300 ℃, introducing nitrogen to dry the magnesium chromium oxide, cooling to 150 ℃ after drying for 8h, and introducing N2Partially fluorinating the magnesium chromium oxide with mixed gas with the volume ratio of HF to the mixed gas being 10:1 and the gas flow rate being 100ml/min for 2h, and then adding N2The volume ratio of HF/Mg to Cr is adjusted to 5:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2The volume ratio of HF/Mg to Cr is adjusted to 3:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2Adjusting the volume ratio of/HF to 1:1, and keeping the gas flow rate at 100ml/min to continuously perform partial fluorination on the magnesium-chromium oxide, wherein the fluorination time is 2h, and the fluorination is finished to obtain the partially fluorinated chromium-doped aluminum fluoride magnesium oxide catalyst.
Reducing the temperature to 75 ℃, uniformly mixing 1L of wastewater with the ammonia nitrogen content of 15ppm and 0.18g of hydrogen peroxide with the mass concentration of 25%, enabling the mixed ammonia nitrogen wastewater to flow through a fixed bed reactor at the flow rate of 100ml/min by using a peristaltic pump for catalytic oxidation (adopting 20g of the above fluorine-alumina magnesium catalyst), actually measuring the ammonia nitrogen concentration of 4.5ppm (according to the method of comparative example 1), and measuring NH (NH) in the discharged ammonia nitrogen wastewater4+The conversion rate of-N reaches 70 percent, and NO in the wastewater after the treatment is detected by ion chromatography3-It was not detected.
Example 2
Dissolving 94g of magnesium chloride and 15.8g of chromium trichloride in 1L of pure water, slowly adding ammonia water to the solution until the pH value is 10, continuously stirring the solution for reaction for 30min, filtering the solution to obtain a mixture of magnesium oxide and chromium oxide, precipitating the solution to obtain powder, adding 1g of 400-mesh silica gel into the powder, uniformly mixing the powder and the powder, and granulating the powder by using a granulator to obtain magnesium-chromium oxide particles (the diameter is 1.5mm, and the height is 2 mm).
Placing 20g of the obtained magnesium chromium oxide particles in a fixed bed reactor, heating to 300 ℃, introducing nitrogen to dry the magnesium chromium oxide, cooling to 150 ℃ after drying for 8h, and introducing N2Partially fluorinating the magnesium chromium oxide with mixed gas with the volume ratio of HF to the mixed gas being 10:1 and the gas flow rate being 100ml/min for 2h, and then adding N2The volume ratio of HF/Mg to Cr is adjusted to 5:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2The volume ratio of HF/Mg to Cr is adjusted to 3:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2Adjusting the volume ratio of/HF to 1:1, and keeping the gas flow rate at 100ml/min to continuously perform partial fluorination on the magnesium-chromium oxide, wherein the fluorination time is 2h, and the fluorination is finished to obtain the partially fluorinated chromium-doped aluminum fluoride magnesium oxide catalyst.
Reducing the temperature to 75 ℃, uniformly mixing 1L of wastewater with the ammonia nitrogen content of 15ppm and 1g of sodium hypochlorite with the mass concentration of 10%, enabling the mixed ammonia nitrogen wastewater to flow through a fixed bed reactor at the flow rate of 100ml/min by using a peristaltic pump for catalytic oxidation (by adopting 20g of the above fluoroaluminate magnesium catalyst), and actually measuring the ammonia nitrogen concentration of 6ppm (detected according to the method of comparative example 1) in the discharged ammonia nitrogen wastewater, wherein the NH concentration is measured4+The conversion rate of-N reaches 53 percent, and NO in the wastewater after the treatment is detected by ion chromatography3-It was not detected.
Example 3
Dissolving 94g of magnesium chloride and 15.8g of chromium trichloride in 1L of pure water, slowly adding ammonia water to the solution until the pH value is 10, continuously stirring the solution for reaction for 30min, filtering the solution to obtain a mixture of magnesium oxide and chromium oxide, precipitating the solution to obtain powder, adding 1g of 400-mesh silica gel into the powder, uniformly mixing the powder and the powder, and granulating the powder by using a granulator to obtain magnesium-chromium oxide particles (the diameter is 1.5mm, and the height is 2 mm).
Placing 20g of the obtained magnesium chromium oxide particles in a fixed bed reactor, heating to 300 ℃, introducing nitrogen to dry the magnesium chromium oxide, cooling to 150 ℃ after drying for 8h, and introducing N2Partially fluorinating the magnesium chromium oxide with mixed gas with the volume ratio of HF to the mixed gas being 10:1 and the gas flow rate being 100ml/min for 2h, and then adding N2The volume ratio of HF/Mg to Cr is adjusted to 5:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2The volume ratio of HF/Mg to Cr is adjusted to 3:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2Adjusting the volume ratio of/HF to 1:1, and keeping the gas flow rate at 100ml/min to continuously perform partial fluorination on the magnesium-chromium oxide, wherein the fluorination time is 2h, and the fluorination is finished to obtain the partially fluorinated chromium-doped aluminum fluoride magnesium oxide catalyst.
Reducing the temperature to 75 ℃, enabling 1L of wastewater with the ammonia nitrogen content of 15ppm to flow through a fixed bed reactor by a peristaltic pump at the flow rate of 100ml/min, and simultaneously introducing oxygen into the fixed bed reactor for catalytic oxidation (by adopting 20g of the above fluorine-containing aluminum magnesium oxide catalyst), wherein the flow rate of the oxygen is 30ml/min, the actual measurement of the ammonia nitrogen concentration of the discharged ammonia nitrogen wastewater is 11ppm (detected according to the method of comparative example 1), and NH (ammonia nitrogen) is detected4+The conversion rate of-N reaches 27 percent, and NO in the wastewater after the treatment is detected by ion chromatography3-It was not detected.
Example 4
Dissolving 94g of magnesium chloride and 15.8g of chromium trichloride in 1L of pure water, slowly adding ammonia water to the solution until the pH value is 10, continuously stirring the solution for reaction for 30min, filtering the solution to obtain a mixture of magnesium oxide and chromium oxide, precipitating the solution to obtain powder, adding 1g of 400-mesh silica gel into the powder, uniformly mixing the powder and the powder, and granulating the powder by using a granulator to obtain magnesium-chromium oxide particles (the diameter is 1.5mm, and the height is 2 mm).
Placing 20g of the obtained magnesium chromium oxide particles in a fixed bed reactor, heating to 300 ℃, introducing nitrogen to dry the magnesium chromium oxide, cooling to 150 ℃ after drying for 8h, and introducing N2Partially fluorinating the magnesium-chromium oxide with mixed gas with a volume ratio of HF to HF of 10:1 and a gas flow rate of 100ml/min for 2h, and thenThen N is2The volume ratio of HF/Mg to Cr is adjusted to 5:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2The volume ratio of HF/Mg to Cr is adjusted to 3:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2Adjusting the volume ratio of/HF to 1:1, and keeping the gas flow rate at 100ml/min to continuously perform partial fluorination on the magnesium-chromium oxide, wherein the fluorination time is 2h, and the fluorination is finished to obtain the partially fluorinated chromium-doped aluminum fluoride magnesium oxide catalyst.
Reducing the temperature to 75 ℃, uniformly mixing 1L of wastewater with the ammonia nitrogen content of 15ppm and 0.18g of hydrogen peroxide with the mass concentration of 25%, enabling the mixed ammonia nitrogen wastewater to flow through a fixed bed reactor at the flow rate of 50ml/min by using a peristaltic pump for catalytic oxidation (adopting 20g of the above fluoroaluminate magnesium catalyst), actually measuring the ammonia nitrogen concentration of 4ppm (detected according to the method of comparative example 1) in the discharged ammonia nitrogen wastewater, and measuring NH (NH) content4+The conversion rate of-N reaches 73 percent, and NO in the wastewater after the treatment is detected by ion chromatography3-It was not detected.
Example 5
Dissolving 94g of magnesium chloride and 15.8g of chromium trichloride in 1L of pure water, slowly adding ammonia water to the solution until the pH value is 10, continuously stirring the solution for reaction for 30min, filtering the solution to obtain a mixture of magnesium oxide and chromium oxide, precipitating the solution to obtain powder, adding 1g of 400-mesh silica gel into the powder, uniformly mixing the powder and the powder, and granulating the powder by using a granulator to obtain magnesium-chromium oxide particles (the diameter is 1.5mm, and the height is 2 mm).
Placing 20g of the obtained magnesium chromium oxide particles in a fixed bed reactor, heating to 300 ℃, introducing nitrogen to dry the magnesium chromium oxide, cooling to 150 ℃ after drying for 8h, and introducing N2Partially fluorinating the magnesium chromium oxide with mixed gas with the volume ratio of HF to the mixed gas being 10:1 and the gas flow rate being 100ml/min for 2h, and then adding N2The volume ratio of HF/Mg to Cr is adjusted to 5:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2The volume ratio of HF/Mg to Cr is adjusted to 3:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2The volume ratio of HF to the mixture is adjusted to1:1, and continuing to perform partial fluorination on the magnesium-chromium oxide at the gas flow rate of still 100ml/min for 2h, and finishing the fluorination to obtain the partially fluorinated chromium-doped magnesium aluminum fluoride catalyst.
Reducing the temperature to 50 ℃, uniformly mixing 1L of wastewater with the ammonia nitrogen content of 15ppm and 0.18g of hydrogen peroxide with the mass concentration of 25%, enabling the mixed ammonia nitrogen wastewater to flow through a fixed bed reactor at the flow rate of 100ml/min by using a peristaltic pump for catalytic oxidation (adopting 20g of the above fluorine-alumina magnesium catalyst), actually measuring the ammonia nitrogen concentration of 6.5ppm (according to the method of comparative example 1), and measuring NH (NH) in the discharged ammonia nitrogen wastewater4+The conversion rate of-N reaches 57 percent, and NO in the wastewater after the treatment is detected by ion chromatography3 -It was not detected.
Example 6
Dissolving 94g of magnesium chloride, 15.8g of chromium trichloride and 0.15g of lanthanum nitrate in 1L of pure water, slowly adding ammonia water to the solution until the pH value is 10, continuously stirring the solution for reaction for 30min, filtering the solution to obtain precipitated powder of a mixture of magnesium oxide, chromium oxide and lanthanum oxide, adding 1g of 400-mesh silica gel into the precipitated powder, uniformly mixing the mixture, and granulating the mixture by using a granulator to obtain magnesium-chromium-lanthanum oxide particles (the diameter is 1.5mm, and the height is 2 mm).
Placing 20g of the obtained magnesium chromium lanthanum oxide particles in a fixed bed reactor, heating to 300 ℃, introducing nitrogen to dry the magnesium chromium lanthanum oxide, cooling to 150 ℃ after drying for 8h, and introducing N2Partially fluorinating the magnesium-chromium-lanthanum oxide with mixed gas with the volume ratio of HF to HF being 10:1 and the gas flow rate being 100ml/min for 2h, and then adding N2The volume ratio of HF/Mg to Cr to La is adjusted to 5:1, the gas flow rate is still 100ml/min, the partial fluorination is continued for 2h, and then N is added2The volume ratio of HF/Mg to Cr to La is adjusted to 3:1, the gas flow rate is still 100ml/min, the partial fluorination is continued for 2h, and then N is added2Adjusting the volume ratio of/HF to 1:1, and keeping the gas flow rate at 100ml/min to continuously perform partial fluorination on the magnesium chromium lanthanum compound, wherein the fluorination time is 2h, and the fluorination is finished to obtain the partially fluorinated chromium lanthanum doped magnesium oxyfluoride catalyst.
Reducing the temperature to 75 ℃, and reducing the ammonia nitrogen content of the waste with 15ppm1L of water and 0.18g of hydrogen peroxide with the mass concentration of 25 percent are uniformly mixed, the mixed ammonia nitrogen wastewater flows through a fixed bed reactor at the flow rate of 100ml/min by a peristaltic pump for catalytic oxidation (20 g of the above-mentioned fluorine-aluminum-magnesium catalyst is adopted), the ammonia nitrogen concentration of the discharged ammonia nitrogen wastewater is actually measured to be 3ppm (detected according to the method of comparative example 1), and NH is added4+The conversion rate of-N reaches 80 percent, and NO in the wastewater after the treatment is detected by ion chromatography3-It was not detected.
Example 7
Dissolving 94g of aluminum trichloride, 16g of ferric trichloride and 0.5g of cobalt chloride in 1L of pure water, slowly adding ammonia water to the solution until the pH value is 10, continuously stirring the solution for reaction for 30min, filtering the solution to obtain precipitated powder of a mixture of magnesium oxide, iron oxide and cobalt oxide, adding 1g of 400-mesh silica gel into the precipitated powder, uniformly mixing the mixture, and granulating the mixture by using a granulator to obtain magnesium-iron-cobalt oxide particles (the diameter is 1.5mm, and the height is 2 mm).
Placing 20g of the obtained magnesium iron cobalt oxide particles in a fixed bed reactor, firstly heating to 300 ℃, introducing nitrogen to dry the magnesium iron cobalt oxide, cooling to 150 ℃ after drying for 8h, and introducing N2Partially fluorinating the magnesium iron cobalt oxide with mixed gas with the volume ratio of HF to the mixed gas of 10:1 and the gas flow rate of 100ml/min for 2h, and then adding N2The volume ratio of HF/Mg to Fe to Co is adjusted to 5:1, the gas flow rate is still 100ml/min, partial fluorination is carried out continuously, the fluorination time is 2h, and then N is added2The volume ratio of HF/Mg to Fe to Co is adjusted to be 3:1, the gas flow rate is still 100ml/min, partial fluorination is carried out continuously, the fluorination time is 2h, and then N is added2And adjusting the volume ratio of/HF to 1:1, and keeping the gas flow rate at 100ml/min to continuously perform partial fluorination on the magnesium-iron-cobalt oxide, wherein the fluorination time is 2h, and the fluorination is finished to obtain the partially fluorinated iron-cobalt doped magnesium oxyfluoride catalyst.
Reducing the temperature to 75 ℃, uniformly mixing 1L of wastewater with the ammonia nitrogen content of 15ppm and 0.18g of hydrogen peroxide with the mass concentration of 25%, enabling the mixed ammonia nitrogen wastewater to flow through a fixed bed reactor at the flow rate of 100ml/min by using a peristaltic pump for catalytic oxidation (adopting 20g of the above aluminum fluoride magnesium catalyst), and actually measuring the ammonia nitrogen concentration of 5ppm in the discharged ammonia nitrogen wastewater (according to the method of comparative example 1)Line detection), NH4+The conversion rate of-N reaches 67 percent, and NO in the wastewater after the treatment is detected by ion chromatography3-It was not detected.
Example 8
Dissolving 94g of aluminum trichloride, 16g of zinc chloride and 0.5g of zirconium chloride in 1L of pure water, slowly adding ammonia water to the solution until the pH value is 10, continuously stirring the solution for reaction for 30min, filtering the solution to obtain precipitated powder of a mixture of magnesium oxide, zinc oxide and zirconium oxide, adding 1g of 400-mesh silica gel into the precipitated powder, uniformly mixing the mixture, and granulating the mixture by using a granulator to obtain magnesium-zinc-zirconium oxide particles (the diameter is 1.5mm, and the height is 2 mm).
Placing 20g of the obtained magnesium-zinc-zirconium oxide particles in a fixed bed reactor, heating to 300 ℃, introducing nitrogen to dry the magnesium-zinc-zirconium oxide, cooling to 150 ℃ after drying for 8h, and introducing N2Partially fluorinating the magnesium-zinc-zirconium oxide with mixed gas with the volume ratio of HF to HF of 10:1 and the gas flow rate of 100ml/min for 2h, and then adding N2The volume ratio of HF/Mg-Zn-Zr oxide is adjusted to 5:1, the gas flow rate is still 100ml/min, partial fluorination is continued for 2h, and then N is added2The volume ratio of HF/Mg-Zn-Zr oxide is adjusted to be 3:1, the gas flow rate is still 100ml/min, partial fluorination is carried out on the magnesium-Zn-Zr oxide for 2h, and then N is added2Adjusting the volume ratio of/HF to 1:1, and keeping the gas flow rate at 100ml/min to continuously perform partial fluorination on the magnesium-zinc-zirconium oxide, wherein the fluorination time is 2h, and the fluorination is finished to obtain the partially fluorinated zinc-zirconium doped magnesium oxyfluoride catalyst.
Reducing the temperature to 75 ℃, uniformly mixing 1L of wastewater with the ammonia nitrogen content of 15ppm and 0.18g of hydrogen peroxide with the mass concentration of 25%, enabling the mixed ammonia nitrogen wastewater to flow through a fixed bed reactor at the flow rate of 100ml/min by using a peristaltic pump for catalytic oxidation (adopting 20g of the above fluorine-alumina magnesium catalyst), actually measuring the ammonia nitrogen concentration of 7.5ppm (detected according to the method of comparative example 1) in the discharged ammonia nitrogen wastewater, and measuring NH (NH) content4+The conversion rate of-N reaches 50%, and NO in the wastewater after the treatment is detected by ion chromatography3 -It was not detected.
The ammonia nitrogen wastewater treatment method provided by the invention has the advantages of high ammonia nitrogen removal efficiency, simple process, no secondary pollution and conventional methodAlumina (Al)2O3) The invention adopts magnesium oxyfluoride base catalyst with better performance to catalyze ozone, does not need ozone, adopts conventional hydrogen peroxide, sodium hypochlorite and air, greatly shortens the time of oxidizing and decomposing ammonia nitrogen, and can reach NH only by about 20S of contact time4+The conversion rate of-N reaches more than 60 percent, and almost NO NO is contained in the ammonia nitrogen decomposition products3 -。
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. A method for removing ammonia nitrogen by catalytic oxidation of novel magnesium-based oxyfluoride comprises the following steps:
treating ammonia nitrogen wastewater by adopting novel magnesium-based oxyfluoride and oxidant for catalytic oxidation;
the preparation method of the novel magnesium-based oxyfluoride comprises the following steps:
dissolving magnesium chloride and doped metal element salt in water to adjust the pH value to obtain a mixture;
mixing the mixture with silica gel and granulating to obtain granules;
fluorinating the particles to obtain the novel magnesium-based oxyfluoride compound.
2. The method according to claim 1, wherein the pH is 9 to 11.
3. The method of claim 1, wherein the gas used in the fluorination process comprises:
N2and HF.
4. The method according to claim 1, wherein the oxidant is selected from one or more of hydrogen peroxide, sodium hypochlorite, oxygen and air.
5. The method as claimed in claim 1, wherein the method for removing ammonia nitrogen by catalytic oxidation of the novel magnesium-based oxyfluoride comprises the following steps:
the novel magnesium-based oxyfluoride is filled in a fixed bed reactor, an oxidant and ammonia nitrogen wastewater are mixed, and the obtained mixed solution is subjected to catalytic oxidation treatment on the ammonia nitrogen wastewater through the fixed bed reactor.
6. The method according to claim 5, wherein the amount of the novel magnesium-based oxyfluoride is 15 to 25 g.
7. The method of claim 5, wherein the fixed bed reactor has a diameter of 0.8 to 1.2 inches; the length of the fixed bed is 55-65 cm.
8. The method according to claim 5, wherein the flow rate of the mixed liquid passing through the fixed bed reactor is 80-120 ml/min.
9. The method as claimed in claim 1, wherein the method for removing ammonia nitrogen by catalytic oxidation of the novel magnesium-based oxyfluoride comprises the following steps:
suspending the novel magnesium-based oxyfluoride in ammonia nitrogen wastewater, mixing an oxidant and the ammonia nitrogen wastewater, and stirring to obtain a mixed solution for carrying out catalytic oxidation treatment on the ammonia nitrogen wastewater.
10. The method according to claim 1, wherein the temperature of the catalytic oxidation treatment is 70 to 80 ℃.
CN202111533689.0A 2021-12-15 2021-12-15 Method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride Active CN114229985B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111533689.0A CN114229985B (en) 2021-12-15 2021-12-15 Method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111533689.0A CN114229985B (en) 2021-12-15 2021-12-15 Method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride

Publications (2)

Publication Number Publication Date
CN114229985A true CN114229985A (en) 2022-03-25
CN114229985B CN114229985B (en) 2023-09-19

Family

ID=80756275

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111533689.0A Active CN114229985B (en) 2021-12-15 2021-12-15 Method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride

Country Status (1)

Country Link
CN (1) CN114229985B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641413A (en) * 1995-10-27 1997-06-24 Zimpro Environmental, Inc. Removal of nitrogen from wastewaters
JP2007083233A (en) * 2005-09-23 2007-04-05 Ulsan Chemical Co Ltd Catalyst for producing pentafluoroethane and method for manufacturing the catalyst
CN102886271A (en) * 2012-07-18 2013-01-23 常州大学 Method for preparing catalyst for assisting in converting ammonia nitrogen in circuit board sewage
US20130313199A1 (en) * 2012-05-23 2013-11-28 High Sierra Energy, LP System and method for treatment of produced waters
CN104445577A (en) * 2014-11-04 2015-03-25 江西理工大学 Process for treating ammonia-nitrogen wastewater with medium and low concentration through catalytic ozonation of metallic oxides
CN106430846A (en) * 2016-11-18 2017-02-22 新疆环境工程技术有限责任公司 Efficient treatment integrated process for recalcitrant wastewater with low organic matter content
CN109250842A (en) * 2018-10-09 2019-01-22 北京朗新明环保科技有限公司 A kind of method and process system of fluorine-containing industrial waste water with high ammoniac nitrogen circular treatment
CN110104864A (en) * 2019-06-06 2019-08-09 盛隆资源再生（无锡）有限公司 A kind of processing method of the fluorine-containing ammonia-containing water of acid phosphorus acid type
CN111777628A (en) * 2020-07-13 2020-10-16 江西省科学院应用化学研究所 Catalytic wet oxidation catalyst for treating glyphosate wastewater, and synthesis method and application thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641413A (en) * 1995-10-27 1997-06-24 Zimpro Environmental, Inc. Removal of nitrogen from wastewaters
JP2007083233A (en) * 2005-09-23 2007-04-05 Ulsan Chemical Co Ltd Catalyst for producing pentafluoroethane and method for manufacturing the catalyst
US20130313199A1 (en) * 2012-05-23 2013-11-28 High Sierra Energy, LP System and method for treatment of produced waters
CN102886271A (en) * 2012-07-18 2013-01-23 常州大学 Method for preparing catalyst for assisting in converting ammonia nitrogen in circuit board sewage
CN104445577A (en) * 2014-11-04 2015-03-25 江西理工大学 Process for treating ammonia-nitrogen wastewater with medium and low concentration through catalytic ozonation of metallic oxides
CN106430846A (en) * 2016-11-18 2017-02-22 新疆环境工程技术有限责任公司 Efficient treatment integrated process for recalcitrant wastewater with low organic matter content
CN109250842A (en) * 2018-10-09 2019-01-22 北京朗新明环保科技有限公司 A kind of method and process system of fluorine-containing industrial waste water with high ammoniac nitrogen circular treatment
CN110104864A (en) * 2019-06-06 2019-08-09 盛隆资源再生（无锡）有限公司 A kind of processing method of the fluorine-containing ammonia-containing water of acid phosphorus acid type
CN111777628A (en) * 2020-07-13 2020-10-16 江西省科学院应用化学研究所 Catalytic wet oxidation catalyst for treating glyphosate wastewater, and synthesis method and application thereof

Also Published As

Publication number Publication date
CN114229985B (en) 2023-09-19

Similar Documents

Publication Publication Date Title
CN102276095B (en) Method for degrading organic pollutants in water by gradient ozone catalytic oxidation
EP0211530B1 (en) Effluent treatment
CN100575277C (en) A kind ofly utilize Fe °/TiO 2The method of nitrate nitrogen in the photo catalytic reduction water
CN101643266A (en) Method for mineralizing and degrading organic waste water and processing equipment
CN102381811B (en) Method for removing pollutants in water through stepwise catalytic oxidation-biological activated carbon-ultraviolet (UV) combination
CN101654297A (en) Method and equipment for mineralizing and degrading organic wastewater
CN102040275A (en) Catalysis wet-type oxidation treatment method for cyanogen-containing wastewater
CN100443418C (en) Catalytic ozonization water treatment method
CN102874914A (en) Method for removing pollutants from drinking water by using supported ruthenium catalyst
CN103508548A (en) Water treatment method utilizing heterogeneous catalytic oxidation of permanganate
CN104445577A (en) Process for treating ammonia-nitrogen wastewater with medium and low concentration through catalytic ozonation of metallic oxides
CN114229985B (en) Method for removing ammonia nitrogen by catalytic oxidation of magnesium-based oxyfluoride
KR101404597B1 (en) Nitrate reduction by maghemite supported Cu-Pd bimetallic catalyst
CN114084948B (en) Method for removing ammonia nitrogen by catalytic oxidation
CN204151126U (en) Utilize the specific equipment of multi-metal oxygen race catalyst degradation unsymmetrical dimethyl hydrazine
CN114054052B (en) Method for removing ammonia nitrogen by catalytic oxidation of chromium oxyfluoride
CN106000399A (en) Catalyst decomposable with a trace amount of hydrogen peroxide at normal temperature
CN115321660A (en) Method for selectively removing organic pollutants by transition metal oxide activated chlorite
JP2010149050A (en) Solid catalyst for treating nitrate nitrogen-containing water and method of treating nitrate nitrogen-containing water using the catalyst
Tennakone et al. Photoreduction of dinitrogen to ammonia by ultrafine particles of iron hydroxide oxide (Fe (O) OH) formed by photohydrolysis of iron (II) bicarbonate
Zhang et al. Experimental study on three additives used for the removal of nitrite, a byproduct of ozone oxidation denitration technology
CN102757146A (en) Method for treating coal pressure gasification wastewater by employing coagulation-photocatalytic degradation
CN201354338Y (en) Treatment equipment for mineralizing and degrading organic wastewater
JPH081172A (en) Treatment of ammonia nitrogen-containing water
CN217567821U (en) Concentrated hydrochloric acid purification and iron removal device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant