CN100460567C - Metal modified active carbon fiber electrode and method for removing nitrate thereby - Google Patents
Metal modified active carbon fiber electrode and method for removing nitrate thereby Download PDFInfo
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- CN100460567C CN100460567C CNB2004100985902A CN200410098590A CN100460567C CN 100460567 C CN100460567 C CN 100460567C CN B2004100985902 A CNB2004100985902 A CN B2004100985902A CN 200410098590 A CN200410098590 A CN 200410098590A CN 100460567 C CN100460567 C CN 100460567C
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Abstract
The invention, belonging to water treatment technical field, discloses the electric pole used for removing nitrate in water. The invention uses one of noble metals (palladium, platinum, gold, rhodium, and ruthenium) and one of non noble metals (copper, tin, indium, zinc and silver) to modify the activated carbon fiber and make the electric pole. The method uses the said electric pole as negative pole, and uses graphite and lead oxide as anode, deoxidizing the nitrate at the condition of energisation. The electric pole is cheap and high activity, and the invention is simple operation, convenient management and suits for small-scale decentralized feedwater treatment.
Description
Invention field
The present invention relates to a kind of method of removing the electrode of nitrate in the water and using nitrate in this electrode removal water, it specifically is a kind of metal-modified Activated Carbon Fiber Electrodes, under the situation of energising,, belong to the Application Areas of water technology with the nitrate reduction in the water.
Background of invention
Owing to being extensive use of and the reasons such as a large amount of dischargings of municipal effluent and trade effluent of agrochemical, causing global pollution of nitrate nitrogen in underground water, and be the trend that goes from bad to worse.At present, the most of areas of China are subjected to azotate pollution to some extent as the underground water of drinking water source, and its concentration of indivedual areas has surpassed 100mg-N/L.The nitrate of Excessive Intake has a lot of harm to HUMAN HEALTH, can cause methemoglobinemia, can cause hypoxia death when serious.And effect such as that the inferior ammonium nitrate that forms in the nitrate conversion process etc. also have is carcinogenic, teratogenesis and mutagenesis.Therefore the pollution of nitrate nitrogen in the purifying drinking water becomes crucial environmental problem.
The method of removing nitrate in the water at present mainly contains physics method, biological denitrification method and chemical reduction method.The physics method is the nitrate in the former water to be shifted or concentrate, and in fact it is not removed up hill and dale, so be subjected to certain restriction on using; The biological denitrification method is converted into nitrogen by the reductive action of microorganism with nitrate, is present main method of denitration, but still the shortcoming that exists some to be difficult to overcome, low as capacity of resisting impact load, have secondary pollution, complex process is not suitable on a small scale and disperses to water treatment etc.Chemical reduction method comprises metal simple-substance reduction method, hydrogen catalysis reduction method and electrochemical reducing.The metal simple-substance reduction method is to be that reductive agent is a nitrogen with nitrate reduction with metal simple-substances such as iron, aluminium, zinc, and its reaction conditions is difficult to control, easily produces by product and causes secondary pollution.The hydrogen catalysis reduction method is to be reductive agent with hydrogen, under the effect of catalyzer nitrate is reduced, and its speed of response is fast, can avoid the secondary pollution to water.But the solubleness of hydrogen in water is low, and inflammable and explosive, and the transportation difficulty has inconvenience when using.Electrochemical reducing is a kind of method of denitration that just develops out in recent years, and the present electrode of studying mostly is precious metal material, as palladium, platinum, gold electrode; The perhaps noble metal electrode of surface modification, it costs an arm and a leg, and is difficult to practical application.
Summary of the invention
The objective of the invention is: prepare that a kind of cost is low, high reactivity, in order to removing the metal modified active carbon fiber electrode of nitrate in the water, and utilize this electrode to set up a kind of method of removing nitrate nitrogen in the water safely and efficiently.
Electrode involved in the present invention is to utilize palladium (A) and particle modified activated carbon fiber (ACF) electrode (A-B/ACF) of transition metal tin (B), wherein A:B=1:(0.125-1), A:ACF=1:(20-100) (weight ratio).
Electrode adopts the preparation of iso volumetric impregnation method.At first the corresponding solubility lead compound of the precious metal palladium (A) of metering is dissolved in the hydrochloric acid soln, activated carbon fiber is impregnated in carry out the periodicity stirring in this solution, dipping time is 12-24 hours, and periodically mixing chamber was divided into 1 hour; 105-120 ℃ of oven dry down, drying time is 10-18 hours, calcines 1-3 hours down for 400-500 ℃, be cooled to room temperature, impregnated in then and carry out the periodicity stirring in the gauge water solution that contains transition metal tin (B), dipping time is 12-24 hours, and periodically mixing chamber was divided into 1 hour; Through 105-120 ℃ of oven dry down, drying time is 10-18 hours again, calcines 1-3 hours down for 400-500 ℃, is cooled to room temperature, and with its thoroughly reduction under 200-300 ℃, the recovery time is 1-3 hours at last, and used reducing atmosphere is a hydrogen.
The method of nitrate is as follows in the removal water that the present invention set up:
As negative electrode, graphite, plumbous oxide inactive, conductive material separate with proton exchange membrane between the anode and cathode as anode with the Activated Carbon Fiber Electrodes of prepared palladium metal (A) and tin (B) modification.Under the situation of energising, the electrical catalyze reduction reaction takes place in the water that contains nitrate in the cathodic area, with nitrate reduction; The electrolysis of water or the reaction of carbon dioxide process carbon electrode stripping take place in the positive column.The strength of current that is applied between anode and cathode is 20-60mA, and the initial pH value of institute's treating water is 5-10.
Characteristics of the present invention are:
(1) prepared metal modified active carbon fiber electrode cost is low, the active height of reduction nitrate, and speed of response is fast.
(2) adopt electrochemical method reduction nitrate, need not add any medicament, can avoid going out the water generates secondary pollution.
(3) proton exchange membrane is divided into cathodic area and positive column with reaction, helps at cathodic area formation reductibility environment; Proton can be delivered to the cathodic area from the positive column on the other hand, can cushion the pH value in cathodic area.
(4) technology is simple, and is low to the operational management requirement, is applicable to small-scale and disperses to give water treatment.
Embodiment
Example 1
At first the 0.04619g Palladous chloride is dissolved in the appropriate hydrochloric acid solution, adopt the iso volumetric impregnation method, the 0.554g activated carbon fiber is immersed in the above-mentioned Palladous chloride hydrochloric acid soln, carry out periodicity and stir, through 105 ℃ of oven dry 12 hours, under argon shield, calcined 2 hours again in 500 ℃; After naturally cooling to room temperature, impregnated in again in an amount of tin chloride hydrochloric acid soln, make Sn/ACF=1.25% (weight ratio), carry out periodicity and stir,, under argon shield, calcined 2 hours again in 500 ℃ through 105 ℃ of oven dry 12 hours; After naturally cooling to room temperature, be reductive agent with hydrogen, promptly get metal-modified Activated Carbon Fiber Electrodes at 200 ℃ of following reductase 12s hour.
Adopt this electrode as the nitrate in the cathodic reduction water, the useful volume 400mL in cathodic area, electrode area 36cm
2, anode is a graphite, and annode area equals cathode area, and received current intensity is 40mA.Cathodic area nitrate radical starting point concentration is 110mg/L, and initial pH is 7.6, after 240min is carried out in reaction, and nitrate concentration 3.4mg/L, nitrite anions concentration 3mg/L, ammonium concentration 4.7mg/L.
Example 2
Electrode preparation and use this electrode to remove the method such as the example 1 of nitrate in water, different is Sn/ACF=2.5% (weight ratio) wherein.Cathodic area nitrate radical starting point concentration is 110mg/L, and initial pH is 7.6, after 240min is carried out in reaction, and nitrate concentration 8.37mg/L, nitrite anions concentration 3.1mg/L, ammonium concentration 8.6mg/L.
Example 3
Electrode preparation and this electrode of use are removed the method such as the example 1 of nitrate in water.Cathodic area nitrate radical starting point concentration is 113mg/L, and initial pH is 5.1, after 240min is carried out in reaction, and nitrate concentration 1.13mg/L, nitrite anions concentration 0.1mg/L, ammonium concentration 4.9mg/L.
Claims (5)
1. electrode of removing nitrate in the water, it is characterized in that, be carrier with activated carbon fiber (ACF), and load has precious metal palladium (A) and base metal tin (B) particle as active constituent on this carrier, A:B=1:(0.125-1 wherein), A:ACF=1:(20-100) (weight ratio).
2. the preparation method of the electrode of nitrate in the described removal water of claim 1, it is characterized in that, corresponding solubility lead compound with precious metal palladium (A) is dissolved in the hydrochloric acid soln earlier, activated carbon fiber be impregnated in carry out periodicity in this solution and stir, dipping time is 12-24 hours, and periodically mixing chamber was divided into 1 hour; 105-120 ℃ of oven dry down, drying time is 10-18 hours, calcines after 1-3 hours down for 400-500 ℃, be cooled to room temperature, impregnated in then and carry out the periodicity stirring in the gauge water solution that contains transition metal tin (B), dipping time is 12-24 hours, and periodically mixing chamber was divided into 1 hour; 105-120 ℃ of down oven dry, drying time is 10-18 hours, 400-500 ℃ down calcining be cooled to room temperature after 1-3 hours, at last under 200-300 ℃ with its thorough reduction, the recovery time is 1-3 hours, used reducing atmosphere is a hydrogen.
3. according to the described preparation method of claim 2, it is characterized in that nitrate, acetate, chlorate that the corresponding solubility lead compound of described precious metal palladium (A) is precious metal palladium (A).
4. the method for nitrate in the electrochemical reduction water, it is characterized in that, with precious metal palladium (A) and the particle modified activated carbon fiber of base metal tin (B) is negative electrode, graphite, plumbous oxide inactive, conductive material are as anode, separate with proton exchange membrane between the anode and cathode, under the condition of airtight anoxia, make the nitrate reduction in the cathode compartment.
5. according to the method for nitrate in the described a kind of electrochemical reduction water of claim 4, it is characterized in that the strength of current that is applied is 20-60mA between anode and cathode, the initial pH value of institute's treating water is 5-10.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100985902A CN100460567C (en) | 2004-12-15 | 2004-12-15 | Metal modified active carbon fiber electrode and method for removing nitrate thereby |
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| CNB2004100985902A CN100460567C (en) | 2004-12-15 | 2004-12-15 | Metal modified active carbon fiber electrode and method for removing nitrate thereby |
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| CN1789498A CN1789498A (en) | 2006-06-21 |
| CN100460567C true CN100460567C (en) | 2009-02-11 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624226B (en) * | 2008-07-11 | 2013-05-08 | 中国科学院生态环境研究中心 | Method and reactor for removing nitrate through catalytic electrochemical biological hydrogen autotrophic denitrification |
| CN101537353B (en) * | 2009-04-29 | 2011-05-11 | 安徽师范大学 | Preparation method of single-dimensional nano composite material |
| CN102039125A (en) * | 2009-10-13 | 2011-05-04 | 中国科学院生态环境研究中心 | Preparation and application method of supported bimetallic catalyst for removing nitrate in water |
| CN101700924B (en) * | 2009-11-30 | 2011-06-29 | 重庆大学 | Device for removing nitrate in water |
| CN102992543B (en) * | 2012-11-27 | 2014-07-23 | 中国科学院沈阳应用生态研究所 | Method and device for biochemically removing nitrate in drinking water |
| CN103304038B (en) * | 2013-05-14 | 2015-03-04 | 南京大学 | Electrochemical-biological membrane synergistic reactor and application thereof in nitrogen-containing organic wastewater |
| CN105000636A (en) * | 2015-07-10 | 2015-10-28 | 中国科学院生态环境研究中心 | Method for removing cyanide from water by using copper electrode strengthened electrochemistry |
| CN107140716B (en) * | 2017-06-22 | 2020-09-01 | 河海大学 | Equipment and method for treating dye wastewater by electrochemical-adsorption composite process |
| CN108751358A (en) * | 2018-07-06 | 2018-11-06 | 广东益诺欧环保股份有限公司 | A kind for the treatment of method and apparatus of high concentrated organic wastewater |
| CN111204848B (en) * | 2020-01-12 | 2021-05-18 | 大连理工大学 | Method for removing pollutants through non-uniform cathodic electro-reduction of metal loaded on conductive substrate |
| CN114106343A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Preparation method of metal organic framework material |
| CN112110522B (en) * | 2020-09-09 | 2022-04-01 | 清华大学 | Electrochemical Fenton device and electrochemical Fenton method for treating pollutants |
| CN114212860B (en) * | 2021-12-14 | 2023-04-25 | 宁波职业技术学院 | Method for treating wastewater by nano-silver modified carbon paper anode electro-active persulfate |
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| US5935392A (en) * | 1995-06-01 | 1999-08-10 | Upscale Water Technologies, Inc. | Electrodes for electrolytic removal of nitrates from water, methods of making same, and apparatus incorporating said electrodes |
| US5958196A (en) * | 1995-06-01 | 1999-09-28 | Upscale Water Technologies, Inc. | Planar carbon fiber and noble metal oxide electrodes and methods of making the same |
| JP2000325956A (en) * | 1999-05-19 | 2000-11-28 | Meidensha Corp | Electrochemical water cleaner |
| JP2004137593A (en) * | 2002-10-17 | 2004-05-13 | Kenji Shinohara | Porous ceramic-water electrode |
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| US5935392A (en) * | 1995-06-01 | 1999-08-10 | Upscale Water Technologies, Inc. | Electrodes for electrolytic removal of nitrates from water, methods of making same, and apparatus incorporating said electrodes |
| US5958196A (en) * | 1995-06-01 | 1999-09-28 | Upscale Water Technologies, Inc. | Planar carbon fiber and noble metal oxide electrodes and methods of making the same |
| JP2000325956A (en) * | 1999-05-19 | 2000-11-28 | Meidensha Corp | Electrochemical water cleaner |
| JP2004137593A (en) * | 2002-10-17 | 2004-05-13 | Kenji Shinohara | Porous ceramic-water electrode |
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