CN105621759A - Method for efficiently and environmentally removing nitrogen nitrate in water - Google Patents
Method for efficiently and environmentally removing nitrogen nitrate in water Download PDFInfo
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- CN105621759A CN105621759A CN201610010239.6A CN201610010239A CN105621759A CN 105621759 A CN105621759 A CN 105621759A CN 201610010239 A CN201610010239 A CN 201610010239A CN 105621759 A CN105621759 A CN 105621759A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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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
- C02F2101/163—Nitrates
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for efficiently and environmentally removing nitrogen nitrate in water. The method comprises the following steps: adding an iron and copper dual-metal material and disodium EDTA in wastewater, regulating a pH (Potential of Hydrogen) value of the wastewater, carrying out solid-liquid separation after a stirring reaction, and collecting supernatant for standby use; adding an Na2SO3 solution in the supernatant of which the pH value is regulated, carrying out a second-level reduction reaction and regulating the pH value under a stirring condition, and carrying out the solid-liquid separation, thus obtaining liquid, namely the water in which the nitrogen nitrate is removed. A chemical denitrification technology disclosed by the invention is economic and effective, the nitrogen nitrate in the water is reduced into nitrogen-based harmless matters while the removing rate of the nitrogen nitrate in the water is increased, the pollution of the nitrogen nitrate in the water is completely removed, the cost of raw materials is cheap, the compatibility with the environment is good, environment protection is realized, the preparation method is simple, the operation is convenient, the reaction condition is mild, and the preparation method is suitable for industrial large-scale production.
Description
Technical field
The invention belongs to Environmental Chemistry technical field, be specifically related to a kind of high-efficiency environment friendly and remove the method for nitrate nitrogen in water.
Background technology
In water, nitrate is under aerobic environment, most stable of nitrogen compound in the nitrogen-containing compound of various forms, is also the itrogenous organic substance catabolite through mineralization terminal stage. The toxicity of nitrate own is very low, but it can cause methemoglobinemia after entering human body, may result in hypoxia death time serious. The inferior ammonium nitrate etc. formed in nitrate transformation process also has the effects such as carcinogenic, teratogenesis and mutagenesis. Crop at plant interior accumulation, causes the disease of crop, worm, evil, and affects crop quality after absorbing excessive nitrate from irrigation water. Azotate pollution is suffered in order to reduce water body, efficiently control polluter, the discharge of restriction nitrate nitrogen, the many discharge standards of China such as " urban wastewater treatment firm pollutant emission standard " GB18918-2002, " process hides and fur manufacturing industrial water pollution thing discharge standard " GB30486 2013, " fermentation alcohol and Liquor-making industry pollution discharge standard " GB27631-2011, total nitrogen concentration of emission has been specified by " household refuse landfill sites Environmental capacity standard " GB16889-2008 etc.
In waste water, the removal technology of nitrate nitrogen mainly includes biological denitrification method, physical-chemical process and electronation repairing method. Wherein, although nitrate nitrogen can be separated by the materilization freatment methods such as hyperfiltration, electroosmose process, ion-exchange-resin process from waste water, but the problem that the dense water formed is faced with final process. The fundamental solution solving water body nitrate polluted by nitrogen is to recover the balance of nature Nitrogen Cycling, is reduced to nitrogen by the nitrate nitrogen in waste water; Biological denitrification method is a kind of by facultative anaerobe, by the NO in water3 -And NO2 -By the method that disassimilation is reduced to nitrogen. Biological denitrification method has been widely used for wastewater treatment industry, but have that denitrification rates is slow, operational management cost is high, be not suitable on a small scale and dispersion wastewater treatment, to shortcomings such as the high water treatment effect differences of high salt or bio-toxicity. Compared with biological denitrification, the outstanding advantages of chemical denitrification method has: the denitration speed of unit volume reactor is faster than biological denitrification method; Technique is simple and the requirement of operational management is low; The wastewater treatment suitability is higher.
Chemical denitrification method is a kind of method utilizing chemical reduction reaction that nitrate nitrogen is converted into lower valency nitrogen. Under optimum conditions, chemical denitrification reaction can realize NO3��NO2��NO��N2O��N2��NH4 +Process, and the selection of the form of reduzate and productivity and reducing agent and method of reducing is closely related. Difference according to reducing agent, chemical denitrification method is broadly divided into active metal reducing process and the big class of catalytic reduction method two. Wherein, with the active metal simple substance such as ferrum, aluminum, zinc for reducing agent can nitrate in fast restore water, reaction condition is gentle, easy and simple to handle, report existing more both at home and abroad, wherein Fe0Research more. Reduzate for Fe0 is mainly NH4 +-N, only only small part nitrate is likely to be converted into N2Problem, people have developed iron-series duplex metal catalytic reduction technique in recent years. This technology is in nanometer Fe0In mix metallic catalyst Ni, Cu, Pd etc., bimetallic introducing can further improve N03 -Removal rate and the selectivity of product. In this kind of technology, adopt nano-Fe/Cu to make reducing agent and can improve the productivity of nitrogen in nitrate reduction product and be subject to people's attention. Owing to the Cu catalyst in nano-Fe/Cu bimetallic is to NO2 -There is higher selectivity so that course of reaction has the NO of 40%3 -Intermediate by-products NO can be reduced to2 -, greatly reduce the reduction effect of nitrate nitrogen, the intermediate by-products NO how reduction to be produced2 -It is reduced to harmless nitrogen gas, is the difficult problem that must solve in the application of nano-Fe/Cu method. Additionally, nano-Fe/Cu is mainly the nano-particle of support type, preparing mainly through liquid phase reduction, its preparation condition is harsh, and preparation process is complicated, and preparation cost is higher, is unfavorable for large-scale application.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, it is provided that a kind of with bimetallic for the method for nitrate nitrogen in reducing agent high-efficiency environment friendly removal water.
The purpose of the present invention is achieved through the following technical solutions: a kind of high-efficiency environment friendly removes the method for nitrate nitrogen in water, and it comprises the following steps:
S1. primary reduction: adding iron-copper bi-metal material and disodiumedetate (EDTA-2Na) in waste water, regulate the pH value of waste water, preliminary reduction reaction occurs under agitation, has reacted rear solid-liquid separation, supernatant is standby;
S2. second-stage reduction: add Na in the supernatant regulating pH value2SO3Solution, occurs second-stage reduction to react and regulate pH value, solid-liquid separation when stirring, and gained liquid is the water removing nitrate nitrogen.
Further, described iron-copper bi-metal material adopts following methods to prepare: be placed in by iron plate in the copper-bath that mass fraction is 0.5��2%, carry out displacement reaction 15��25min when solution ph is 3��5, gained solid is iron-copper bi-metal material.
Further, described ferrum is 100:1��100:3 with the mass ratio of copper.
Further, step S1 adopts H2SO4Or NaOH regulates the pH value of waste water to 3��6, the temperature of stirring reaction is 10��40 DEG C, and the response time is 30��60min, and mixing speed is 100��200r/min.
Further, iron-copper bi-metal material described in step S1 is 1500:1��1800:1 with the mass ratio of nitrate nitrogen in waste water, and described EDTA-2Na is 0.5:1��5:1 with the mass ratio of nitrate nitrogen in waste water.
Further, step S2 adopts H2SO4Or the pH value of NaOH adjustment supernatant is 3.5��4.5, adopting NaOH to regulate the pH value of second-stage reduction reaction solution to 6.0��9.0, stirring reaction temperature is 10 ~ 40 DEG C, and the response time is 20��40min, and mixing speed is 100��200r/min.
Further, Na described in step S22SO3It is 1:1��10:1 with the mass ratio of nitrate nitrogen in waste water.
Principles of the invention is: utilize the high surface area supported copper simple substance of ferrum copper displacement reaction and iron plate, forms iron-copper bi-metal material. In the primary reduction process of nitrate wastewater, due to the electrocatalysis of Cu, accelerate Fe �� Fe2+Course of reaction, the electron transmission of generation is to Cu electrode. Utilizing the reaction interface of Cu, nitrate nitrogen obtains electronics on Cu, is reduced to nitrite nitrogen. Further, the present invention reduces while nitrate nitrogen at bimetallic, utilize the Fe (II) in disodiumedetate (EDTA-2Na) solution complexation liquid phase, form EDTA-Fe (II) complex, strengthening the reproducibility of ferrous ion, the nitrite nitrogen produced is reduced, the NO of generation is captured again in the solution, exist with the form of EDTA-Fe (II) NO, it is to avoid the effusion of NO. Thereafter, second-stage reduction process is added reducing agent Na2SO3Fixing EDTA-Fe (II) NO in the liquid phase is reduced to nitrogen.
Reduction process dominant response equation is as follows:
(1) preparation of iron-copper bi-metal material: Fe+Cu2+��Fe2++ Cu;
(2) iron-copper bi-metal one-level reduction reaction:
Anode: Fe �� Fe2++2e-
Negative electrode: NO3 -+2e-��NO2 -; NO2 -+e-��NO
Liquid phase: Fe (II)+NO2 -+2H+��NO+H2O+Fe(III)
EDTA-2Na+Fe(II)��EDTA-Fe(II)+2Na+
EDTA-Fe(II)+NO��EDTA-Fe(II)NO
EDTA-Fe(II)+NO2 -+2H+��NO+H2O+EDTA-Fe(III)
(3) Na2SO3Second-stage reduction is reacted:
EDTA-Fe(II)NO+Na2SO3��Na2SO4+N2+EDTA-Fe(II)
The invention have the advantages that
(1) present invention employs iron-copper bi-metal as one-level reducing agent, its preparation method is simple, anti-nitration reaction speed is fast, iron-copper bi-metal constitutes galvanic couple galvanic element in the solution, the galvanic couple galvanic element potential difference that both metals are constituted, the reduction that can make nitrate nitrogen rests on the nitrite stage, provides support for follow-up reduction reaction;
(2) present invention adopts EDTA-2Na to make reduction auxiliary agent, trapping Fe (II) generates EDTA-Fe (II) complex, the difference in Electrode Potential of ferrum copper can be changed on the one hand, decrease the generation of reduzate ammonia, make reduction-state nitrogen mainly based on nitrite nitrogen; The EDTA-Fe (II) generated on the other hand strengthens Fe (II) and reduces the reducing power of nitrite, the NO of generation can be made fixing in the solution with EDTA-Fe (II) NO form, decrease NO to the release in air, for Na2SO3It is that nitrogen provides guarantee by its drastic reduction;
(3) present invention adopt low in raw material price, being compatible with the environment property end product good, denitrifying based on non-harmful nitrogen, therefore, the advantage that the present invention has green, environmental protection;
(4) preparation method of the present invention is simple, easy to operate, reaction condition is gentle, cost is low, it is adaptable to industrialization large-scale production.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, and protection scope of the present invention is not limited to the following stated.
Embodiment 1: a kind of high-efficiency environment friendly removes the method for nitrate nitrogen in water, and it comprises the following steps:
The mass ratio of S1. primary reduction: be placed in by iron plate in the copper-bath that mass fraction is 1%, ferrum and copper is 100:1.5, carries out displacement reaction 20min when solution ph is 4, and gained solid is iron-copper bi-metal material; Waste water adds iron-copper bi-metal material and EDTA-2Na, iron-copper bi-metal material addition is 1600:1 with the mass ratio of nitrate nitrogen in water, EDTA-2Na is 3:1 with the mass ratio of nitrate nitrogen in waste water, the pH value of waste water is regulated to 5 with NaOH, solid-liquid separation after stirring reaction 45min when 25 DEG C, mixing speed is 150r/min, collects supernatant standby;
S2. second-stage reduction: at H2SO4Regulate pH value to the supernatant of 4, add Na2SO3Solution, Na2SO3Being 5:1 with the mass ratio of nitrate nitrogen in waste water, the temperature stirring of 20 DEG C carries out reduction reaction 30min, and mixing speed is 150r/min, regulates the pH value of second-stage reduction reaction solution to 7.5 with NaOH, and solid-liquid separation, gained liquid is the water removing nitrate nitrogen.
Embodiment 2: a kind of high-efficiency environment friendly removes the method for nitrate nitrogen in water, and it comprises the following steps:
The mass ratio of S1. primary reduction: be placed in by iron plate in the copper-bath that mass fraction is 0.5%, ferrum and copper is 100:1, carries out displacement reaction 15min when solution ph is 3, and gained solid is iron-copper bi-metal material; Waste water adds iron-copper bi-metal material and EDTA-2Na, iron-copper bi-metal material addition is 1800:1 with the mass ratio of nitrate nitrogen in water, EDTA-2Na is 0.5:1 with the mass ratio of nitrate nitrogen in waste water, the pH value of waste water is regulated to 6 with NaOH, solid-liquid separation after stirring reaction 30min when 15 DEG C, mixing speed is 100r/min, collects supernatant standby;
S2. second-stage reduction: at H2SO4Regulate pH value to the supernatant of 3.5, add Na2SO3Solution, Na2SO3Being 1:1 with the mass ratio of nitrate nitrogen in waste water, the temperature stirring of 40 DEG C carries out reduction reaction 20min, and mixing speed is 100r/min, regulates the pH value of second-stage reduction reaction solution to 6.0 with NaOH, and solid-liquid separation, gained liquid is the water removing nitrate nitrogen.
Embodiment 3: a kind of high-efficiency environment friendly removes the method for nitrate nitrogen in water, and it comprises the following steps:
The mass ratio of S1. primary reduction: be placed in by iron plate in the copper-bath that mass fraction is 2%, ferrum and copper is 100:3, carries out displacement reaction 25min when solution ph is 5, and gained solid is iron-copper bi-metal material; Adding iron-copper bi-metal material and EDTA-2Na in waste water, iron-copper bi-metal material addition and the mass ratio of nitrate nitrogen in water are 1500:1, EDTA-2Na is 5:1 with the mass ratio of nitrate nitrogen in waste water, uses H2SO4Solid-liquid separation after stirring reaction 60min when the pH value of adjustment waste water is to 3,40 DEG C, mixing speed is 200r/min, collects supernatant standby;
S2. second-stage reduction: regulate pH value at NaOH and add Na to the supernatant of 4.52SO3Solution, Na2SO3Being 10:1 with the mass ratio of nitrate nitrogen in waste water, the temperature stirring of 10 DEG C carries out reduction reaction 40min, and mixing speed is 200r/min, regulates the pH value of second-stage reduction reaction solution to 9.0 with NaOH, and solid-liquid separation, gained liquid is the water removing nitrate nitrogen.
Embodiment 4: a kind of high-efficiency environment friendly removes the method for nitrate nitrogen in water, and it comprises the following steps:
The mass ratio of S1. primary reduction: be placed in by iron plate in the copper-bath that mass fraction is 1.2%, ferrum and copper is 100:1.8, carries out displacement reaction 22min when solution ph is 4.5, and gained solid is iron-copper bi-metal material; Adding iron-copper bi-metal material and EDTA-2Na in waste water, iron-copper bi-metal material addition and the mass ratio of nitrate nitrogen in water are 1700:1, EDTA-2Na is 3:1 with the mass ratio of nitrate nitrogen in waste water, uses H2SO4Solid-liquid separation after stirring reaction 50min when the pH value of adjustment waste water is to 3.5,30 DEG C, mixing speed is 180r/min, collects supernatant standby;
S2. second-stage reduction: regulate pH value at NaOH and add Na to the supernatant of 4.32SO3Solution, Na2SO3Being 8:1 with the mass ratio of nitrate nitrogen in waste water, the temperature stirring of 25 DEG C carries out reduction reaction 35min, and mixing speed is 180r/min, regulates the pH value of second-stage reduction reaction solution to 8.0 with NaOH, and solid-liquid separation, gained liquid is the water removing nitrate nitrogen.
Experimental example 1:
Nitrate nitrogen in certain wastewater from chemical industry, nitrite nitrogen, ammonia-nitrogen content is 80mg/L respectively, 0mg/L, 1.5mg/L, pH is 6, this waste water 5L is collected in the container 1 of 10L acid and alkali-resistance, (iron-copper bi-metal length of a film is 10mm to add iron-copper bi-metal sheet in container 1, width is 4mm, thickness is 0.1mm, iron-copper bi-metal sheet is 4 by iron plate at pH value of solution, ferrum copper mass is immersed in than when for 100:1.5 in the copper-bath that mass fraction is 1%, dipping 20min is prepared from) 675g, add disodiumedetate (EDTA-2Na) 1.86g, with the pH of sulfuric acid regulation solution to 3.5, it is under 150r/min, carry out primary reduction reaction 30min at 15 DEG C and mixing speed, primary reduction is reacted water outlet and is collected in the container 2 that volume is 10L and acid and alkali-resistance, 3.78gNa is added in container 22SO3, regulating the pH to 3.5 of solution, be under 160r/min, carry out second-stage reduction reaction 20min at 25 DEG C and mixing speed, the pH value regulating second-stage reduction reaction solution with NaOH is 6.1, and solid-liquid separation, supernatant is water outlet. Mensuration processes content 0mg/L, 0mg/L, the 1.9mg/L respectively of nitrate nitrogen in water outlet, nitrite nitrogen, ammonia nitrogen, and the clearance of nitrate nitrogen reaches 100%, and in chemical denitrification end product, the selection rate of non-ammonia nitrogen reaches more than 97%.
Experimental example 2:
Certain town domestic sewage, COD in former water, nitrate nitrogen, nitrite nitrogen, ammonia-nitrogen content is 300mg/L respectively, 3.5mg/L, 0.7mg/L, 30mg/L, raw sewage is after biological contact oxidization treatment, nitrate nitrogen in biological treatment water outlet, nitrite nitrogen, ammonia-nitrogen content respectively content is 41.5mg/L, 0.2mg/L, 0.6mg/L, pH is 5.7, biological treatment water outlet 1L is collected in the container 1 of acid and alkali-resistance of 2L, (iron-copper bi-metal length of a film is 10mm to add iron-copper bi-metal sheet in container 1, width is 4mm, thickness is 0.1mm, iron-copper bi-metal sheet is 4.5 by iron plate at pH value of solution, ferrum copper mass is immersed in than when for 100:3 in the copper-bath that mass fraction is 1%, dipping 20min is prepared from) 69g, add disodiumedetate (EDTA-2Na) 0.03g, with the pH of sulfuric acid regulation solution to 4.2, it is under 110r/min, carry out primary reduction reaction 40min at 20 DEG C and mixing speed, primary reduction is reacted water outlet and is collected in the container 2 that volume is 2L and acid and alkali-resistance, 0.05gNa is added in container 22SO3, regulating the pH to 4 of solution, be under 180r/min, carry out degree of depth denitration reaction 30min at 25 DEG C and mixing speed, the pH value regulating second-stage reduction reaction solution with NaOH is 8.0, and solid-liquid separation, supernatant is water outlet. Mensuration processes content 0mg/L, 0mg/L, the 1.1mg/L respectively of nitrate nitrogen in water outlet, nitrite nitrogen, ammonia nitrogen, and the clearance of nitrate nitrogen reaches 100%, and in chemical denitrification end product, the selection rate of non-ammonia nitrogen reaches more than 98%.
Claims (7)
1. a high-efficiency environment friendly removes the method for nitrate nitrogen in water, it is characterised in that it comprises the following steps:
S1. primary reduction: adding iron-copper bi-metal material and disodiumedetate in waste water, regulate the pH value of waste water, preliminary reduction reaction occurs under agitation, has reacted rear solid-liquid separation, supernatant is standby;
S2. second-stage reduction: add Na in the supernatant regulating pH value2SO3Solution, occurs second-stage reduction to react and regulate pH value, solid-liquid separation when stirring, and gained liquid is the water removing nitrate nitrogen.
2. a kind of high-efficiency environment friendly as claimed in claim 1 removes the method for nitrate nitrogen in water, it is characterized in that, described iron-copper bi-metal material adopts following methods to prepare: be placed in by iron plate in the copper-bath that mass fraction is 0.5��2%, carry out displacement reaction 15��25min when solution ph is 3��5, gained solid is iron-copper bi-metal material.
3. a kind of high-efficiency environment friendly as claimed in claim 2 removes the method for nitrate nitrogen in water, it is characterised in that the mass ratio of described ferrum and copper is 100:1��100:3.
4. a kind of high-efficiency environment friendly as claimed in claim 1 removes the method for nitrate nitrogen in water, it is characterised in that adopt H in step S12SO4Or NaOH regulates the pH value of waste water to 3��6, the temperature of stirring reaction is 10��40 DEG C, and the response time is 30��60min, and mixing speed is 100��200r/min.
5. a kind of high-efficiency environment friendly as claimed in claim 1 removes the method for nitrate nitrogen in water, it is characterized in that, iron-copper bi-metal material described in step S1 is 1500:1��1800:1 with the mass ratio of nitrate nitrogen in waste water, and described disodiumedetate is 0.5:1��5:1 with the mass ratio of nitrate nitrogen in waste water.
6. a kind of high-efficiency environment friendly as claimed in claim 1 removes the method for nitrate nitrogen in water, it is characterised in that adopt H in step S22SO4Or NaOH regulates the pH value of supernatant to 3.5��4.5, adopting NaOH to regulate the pH value of second-stage reduction reaction solution to 6.0��9.0, stirring reaction temperature is 10 ~ 40 DEG C, and the response time is 20��40min, and mixing speed is 100��200r/min.
7. a kind of high-efficiency environment friendly as claimed in claim 1 removes the method for nitrate nitrogen in water, it is characterised in that Na described in step S22SO3It is 1:1��10:1 with the mass ratio of nitrate nitrogen in waste water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109928438A (en) * | 2019-04-01 | 2019-06-25 | 陕西蕴德环保科技有限公司 | A kind of iron series water quality cleansing agent production catalyst removal of nitrogen oxide method |
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| JP2005296743A (en) * | 2004-04-08 | 2005-10-27 | Hideo Hayakawa | Method for removing nitrate nitrogen |
| CN103964550A (en) * | 2014-05-24 | 2014-08-06 | 长安大学 | Method for removing nitrate nitrogen in water body |
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| JP2005296743A (en) * | 2004-04-08 | 2005-10-27 | Hideo Hayakawa | Method for removing nitrate nitrogen |
| CN103964550A (en) * | 2014-05-24 | 2014-08-06 | 长安大学 | Method for removing nitrate nitrogen in water body |
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| LI WANG 等: "Simultaneous absorption of NO and SO2 by FeⅡEDTA combined with Na2SO3 solution", 《CHEMICAL ENGINEERING JOURNAL》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109928438A (en) * | 2019-04-01 | 2019-06-25 | 陕西蕴德环保科技有限公司 | A kind of iron series water quality cleansing agent production catalyst removal of nitrogen oxide method |
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