CN1508074A - Method and apparatus for treating water by catalytic reduction of nano metal-memebrane composite electrode - Google Patents
Method and apparatus for treating water by catalytic reduction of nano metal-memebrane composite electrode Download PDFInfo
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Abstract
The present invention relates to a technique for removing oxidation state pollutant in water body and its equipment. It is characterized by that the nano particles of one noble metal, for example Pd, Pt, Ru and Ir, etc. or nano particles of alloy formed from one the above-mentioned noble metal and one transition metal, for example Cu, Sn, Pb, Zn and Fe, tc. are fixed on one side of proton exchange membrane as cathode, and the inert conductor material, for example active carbon, ruthenium oxide and lead oxide, etc. is fixed on another side of proton exchange membrane as anode so as to form nano metal-proton membrane composite electrode. Under the power-on condition the cathode can reduce and remove the oxidation state pollutant, for example nitrate and halogenated organics in the water.
Description
The present invention relates to a kind of method and apparatus of removing oxidation state pollutent in tap water or the waste water by reduction method, specifically be that a kind of nano electro-catalytic material is fixed on forms combined electrode on the proton exchange membrane material, and then formation electrochemical reactor, negative electrode generation reduction reaction under the situation of energising, the method and apparatus that the oxidation state pollutent in water reduction is removed.
There is a big class to belong to the oxidation state material in the chemical substance of polluted water, more common as nitric nitrogen (nitrate and nitrite etc.), halogenated organic matters or the like.These pollution substances have plenty of and must could thoroughly eliminate by the reductive method, as nitric nitrogen; Have plenty of preferably by reduction method and destroy wherein refractory organics or virose group, make it innoxious or make that product after the reduction is easier further removes such material such as halogenated organic matters by methods such as biochemical reactions.
Nitrate is one of modal pollutent in the present underground water, also may exist in some surface water or industrial sewage.The pollution of nitrate is especially serious in the water bodys such as China's underground water.The nitrate of Excessive Intake all do a lot of harms to the health of human body and animal.The method of removing nitrate in the water at present mainly contains physical chemistry partition method, biological denitrification method and chemical reduction method.The physical chemistry partition method is that the nitrate in the former water is concentrated to method in the waste water, so this is not the method for thorough decontamination, is subjected to a lot of restrictions in application.The biological denitrification method makes nitric nitrogen be converted into nitrogen by the reductive action of biology, is present main method of denitration, and once is considered to the most promising method of denitration.But there is the secondary pollution problem to water outlet such as matrix and bacterium in biological process, and to the having relatively high expectations of operational management, especially is not suitable for middle-size and small-size water treatment.Chemical reduction method is a class method of denitration that just develops out in recent years, mainly contains electrochemical reducing, metal simple-substance reduction method and hydrogen catalysis reduction method.(see " model is refined; Qu Jiuhui; Liu Suoxiang; Meng Guanghui. and nitrate removes in the tap water. Techniques and Equipment for Environmental Pollution Control, 2000,1 (3): 44. " and " model is refined; Huang Xia. and chemical denitrification method removes the nitrate in the underground water. Chinese water supply and drainage; 2001,17 (11): 27. ") though present chemical reduction method does not begin to enter extensive practicality, the speed that the patent of this respect and research paper increase is very fast.
Halogenated organic matters in the water belongs to the most dangerous pollution substance, and these materials often have " three cause " property.The 12 class persistence organic pollutants of generally acknowledging in the world all are halogenated organic matters at present.The halogenated organic matters that appears in the water body both may come from the chemical industry three wastes, agricultural chemicals etc., also can stem from the by product of tap water chlorine disinfectant method.The removal method of the halogenated organic matters in the water is similar a bit to the removal method of nitrate, also mainly is physical chemistry partition method, biological process and chemical method etc.The same with denitration, halogenated organic matters also has only by method biochemistry or chemistry and could thoroughly eliminate.Because this class material often all is difficult to biological degradation or to the toxic effect of microorganism, so the application of biological process has a lot of limitation.The chemistry dehalogenation can be divided into oxidation dehalogenation and reductive dehalogenation two classes.Though can be by some advanced oxidation processes with some halogenated organic matters degradeds, the halogen substituting group itself is in higher oxidation state, and the chemical property of a lot of halogenated organic matters is all very stable, so the effect of removing and very desirable.Method by hydrogenating reduction is a kind of shortcut of dehalogenation.Hydrogen can replace the halogen atom on the halogenated organic matters get off, and on the one hand can eliminate or reduce toxicity, loses on the other hand that the organism of halogen atom is also easier to be additive method (as biological process) degraded.Therefore the patent and the research paper increase of chemical reduction dehalogenation are very fast in recent years.
Under the situation that has catalyzer to exist, the multiple oxidation state pollutent reduction in the water can be removed as reductive agent with hydrogen, and hydrogen is a kind of reductive agent of cleaning, can avoid secondary pollution, therefore become the first-selected reductive agent of chemical reduction water treatment method water.But the solubleness of hydrogen in water is extremely low, and inflammable and explosive, and inconvenience is arranged when using.In reaction, generally all need accurately to control the pH in the reaction microenvironment in addition, but be subjected to the restriction of diffusion mass transfer effect, adopt the method for conventional supported catalyst to be difficult to realization this purpose.This is the one of the main reasons that existing hydrogenation catalyst reduction method is difficult to carry out large-scale application.For this reason, the present invention proposes its device of water technology of a kind of nanometer-membrane electrode catalytic reduction.
The objective of the invention is: the defective that overcomes existing method, electrochemical techniques, nano electro-catalytic technology, proton film composite electrode technology are integrated, set up a kind of water treatment method of reduction method safely and efficiently and device, be used for removing the oxidation state pollutent such as nitrate, halogenated organic matters, heavy metal ion, azo organism of tap water or waste water.
Method of the present invention is as follows:
With the nanoparticle of a kind of precious metal such as palladium, platinum, gold, ruthenium, iridium etc., perhaps will contain the nanoparticle of above-mentioned precious metal and another transition metal such as copper, tin, zinc, lead, iron etc., be fixed on a side of proton exchange membrane, with this side as negative electrode.The granularity of the nanoparticle that is adopted is 1～30nm, and recommending to adopt granularity is the particle of 2～7nm.To have inactive, conductive material such as absorbent charcoal material, ruthenium oxide material, plumbous oxide material and be fixed on the opposite side of proton exchange membrane, and with this side as anode.The proton film has proton conductive.Above-mentioned proton film composite electrode is installed in constitutes nano metal-proton film composite electrode electrical catalyze reduction reactor in the reaction vessel.The proton film composite electrode is separated into cathodic area and positive column with reactor.Processed water passes through from the cathodic area, also injects water simultaneously in the positive column.Under the situation of energising, the electrical catalyze reduction reaction takes place in the cathodic area, and the oxidation state pollutent in the water is reduced.The electrolysis of water takes place in the positive column, and discharge produces oxygen.
Reactor of the present invention as shown in drawings.Nano metal-proton film composite electrode electrical catalyze reduction reactor 1 is made up of reaction vessel 4, nano metal-proton film composite electrode 5 and intake- outlet 3,7,8,10.Fig. 2 is the enlarged diagram of proton film composite electrode 5.Proton film composite electrode 5 is combined by mode shown in Figure 2 by sheet proton exchange membrane 11, current collecting board element 13 and 16, nano metal 14, inert anode material 15, cathode terminal 12 and anode terminal 17.Cathodic current collecting board 13 and anodic current collecting board 16 are the electro-conductive material with water-permeable, can select the carbon fibre material of paper shape.Nano metal 14 is fixed on the cathodic current collecting board 13 with skim,, cathodic current collecting board 13 is connected with cathode terminal 12, form the negative electrode of nanometer-film composite electrode 13 sides that are fixed on proton exchange membrane 11.Inertia is led anode material 15 be fixed on the anodic current collecting board 16,, and anodic current collecting board 16 linked to each other with anode terminal 17, form the anode of nano metal-proton film film composite electrode 16 opposite sides that are fixed on proton exchange membrane 11 with thin layer.Nano metal-proton film composite electrode 5 is installed in the reaction vessel 4, and reaction vessel 4 is separated into cathodic area 6 and positive column 9.Reactor 1 is pressed diagramatic way connect direct supply.Processed water is fed by cathodic area water-in 3, after catalytic reduction reaction takes place in the cathodic area, is flowed out by cathodic area water outlet 7.In order to guarantee that successful reaction carries out, also feed clean water in the positive column, water is injected by the positive column water-in, is flowed out by the positive column water outlet.As the case may be, the water inlet of positive column can be adopted the water outlet in cathodic area.
Characteristics of the present invention are:
(1) electronics is a cleanest a kind of reductive agent, adopts electrochemical method need not add any medicament in reaction process, can avoid the secondary pollution problem to water outlet.Help total system is designed to the pattern of fully automatic operation simultaneously, operational administrative is very easy.
(2) proton exchange membrane has very strong proton conductive, helps improving current density, fast reaction speed on the one hand; Proton can be delivered to negative electrode from anode rapidly on the other hand, and favourable to the pH in the microenvironment of accurate control Nanoalloy surface ten minutes, this point is extremely important for the selectivity that improves catalyzed reaction.
(3) proton exchange film composite electrode height is integrated, two interpolar distances very little (＜5mm), not only help improving the current efficiency of reaction, also make reactor compact more, spatiotemporal efficiency is higher.Also can easily reactor be separated into cathodic area and positive column by the proton exchange film composite electrode, help at cathodic area formation reductibility environment.
(4) electrode process and heterocatalysis process are all very responsive to the surface property of material, Nanoalloy with these two process integration at same Nanosurface, can make the improvement of the process and the electrochemical process generation matter of catalytic reduction, improve the speed of main reaction and reduce the speed of side reaction.
Embodiment one:
The useful volume 5L in reactor cathodic area, electrode area 400cm
2(cathode area equals annode area).
Adopt palladium/copper alloy (Pd of a kind of 2～5nm
0.25Cu
0.75) particle is as the electrode catalyst of cathodic reaction, on the unit surface negative electrode to carry a palladium be 0.025mg/cm
2
Use device of the present invention and handle the water that contains nitrate, the concentration of water inlet nitrate nitrogen is 31mg/L, water inlet pH=6.9,10 ℃ of water temperatures.
The input voltage of reactor is 2.1V, and reactor received current intensity is 8.9A.The hydraulic detention time of reactor is 10min.
Treatment effect:
The concentration of water outlet nitrate nitrogen is 2.85mg/L, and the concentration of nitrite nitrogen is 0.13mg/L in the water outlet, NH in the water outlet
3The concentration of-N is 0.08mg/L.
Calculate according to above-mentioned operating parameter and treatment effect:
(1) total denitration rate is 90.39%.
(2) the denitration speed of unit surface nanometer-proton film composite electrode is 2.10mgNO
3 --N/ (cm
2H).
(3) catalytic activity of nano-electrode catalyzer is 84mgNO
3 --N/ (mgPdh), the catalytic selectivity that nitrate nitrogen is converted into nitrogen is 99.25%.
(4) Fan Ying current efficiency is 91%.
(5) in the current/voltage of input, the power consumption that removes nitrate nitrogen is 19KWh/ (kgNO
3 --N), the power consumption for the treatment of water is 0.623KWh/m
3
Embodiment two: handle the water that contains tetracol phenixin
The useful volume 5L in reactor cathodic area, electrode area 400cm
2(cathode area equals annode area).
Adopt the Pd of a kind of 2～5nm
0.33Sn
0.67Alloying pellet is as the electrode catalyst of cathodic reaction, and year palladium on the unit surface negative electrode is 0.03mg/cm
2
Tetracol phenixin concentration is 200mg/L in the water inlet, and the concentration that is converted to organochlorine is 184.4mg/L.The pH=7.0 of water inlet, 25 ℃ of water temperatures.
The input voltage of reactor is 2.5V, and reactor received current intensity is 12.9A.The water inlet of positive column is the water outlet in cathodic area.
The cathodic area hydraulic detention time is 15min.
Treatment effect: the concentration of organochlorine is 0.60mg/L in the water outlet, and decreasing ratio is 99.67%.
Embodiment three: handle the water that contains nitrate, tetracol phenixin, carbon trichloride, trieline
Reactor cathodic area useful volume 10L, cathode area are 850cm
2, the electrode catalyst of employing is Pd
0.25Cu
0.75, the granularity of catalyzer is 2～5nm.Year palladium amount of negative electrode is 0.025mg/cm
2In the water inlet, the concentration of nitrate nitrogen is 28mg/L, and the concentration of tetracol phenixin is 200 μ g/L, and the concentration of carbon trichloride is 200 μ g/L, and the concentration of trieline is 200 μ g/L.Water inlet pH=7.1,10 ℃ of water temperatures.Adopt the water inlet of the water outlet in cathodic area as the positive column.
The cathodic area hydraulic detention time is 8min.
The input voltage of reactor is 2.5V, and received current density is 19.5A.
Treatment effect:
(1) concentration of water outlet nitrate nitrogen is 4.54mg/L, and the concentration of nitrite nitrogen is 0.09mg/L, and ammonia nitrogen concentration is 0.18mg/L.The decreasing ratio of nitrogen is 82.82%, and the nitrogen transformation efficiency is 98.84%.
(2) concentration of tetracol phenixin is 0.1 in the water outlet, and the concentration of trichloromethane is 0.3 μ g/L, and the concentration of trieline is 15m μ g/L.
Claims (8)
1. a method that removes oxidation state pollutent in tap water or the waste water is characterized in that, applying nano metallic substance-proton film composite electrode electrical catalyze reduction technology makes pollutent be reduced in the cathodic area of electrolytic cell and removes.
2. as the said nano metal of claim 1-proton film composite electrode electrical catalyze reduction technology, it is characterized in that,
The nanoparticle that will contain a kind of precious metal such as palladium, platinum, gold, ruthenium, iridium etc., the Nanoalloy particle that perhaps contains above-mentioned a kind of precious metal and a kind of magnesium-yttrium-transition metal such as copper, lead, tin, zinc, iron etc., be fixed on a side of proton exchange membrane, and, under the situation of energising, make the oxidation state pollutent reduction in the water as the negative electrode of electrolytic cell and the catalyzer of reduction reaction.
3. as right 2 said nanoparticles, it is characterized in that granularity is 1nm～30nm, the recommendation granularity is 2～7nm.
4. an electro-chemical water treatment reactor is characterized in that, with the electrode of nano metal-proton film composite electrode as reactor.
5. as right 4 said nano metal-proton film composite electrodes, it is characterized in that, adhere to inactive, conductive material such as absorbent charcoal material, ruthenium oxide, plumbous oxide etc. at opposite side as right 2 said proton films, and with the anode of this side as combined electrode.
6. as right 4 said water processing reactors, it is characterized in that, utilize reaction vessel to be divided into cathode compartment and anolyte compartment as right 5 said nano metal-proton film composite electrodes.
7. as right 6 said cathode compartments, it is characterized in that comprise water-in and water outlet, processed water is entered by water-in, flow out by water outlet through the reaction back.
8. as right 6 said anolyte compartments, it is characterized in that comprise water-in and water outlet, its water inlet can be adopted the water outlet as right 7 said cathode compartments.
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|---|---|---|---|---|
| CN100432297C (en) * | 2004-12-15 | 2008-11-12 | 中国科学院生态环境研究中心 | Electrode for removing nitrate from water and preparation method thereof |
| CN101346315B (en) * | 2005-10-28 | 2012-06-27 | 阿夸特克股份有限公司 | Highly stable aqueous solution, electrode with nanocoating for preparing the solution and method for making this electrode |
| CN103233242A (en) * | 2013-03-30 | 2013-08-07 | 浙江工业大学 | DSA/Pb alloy composite electrode, its preparation method and application |
| CN104646405A (en) * | 2015-02-15 | 2015-05-27 | 中国科学院生态环境研究中心 | Electrode device and method for lowering arsenic and lead concentrations in rice |
| WO2015154713A1 (en) * | 2014-04-12 | 2015-10-15 | 大连双迪创新科技研究院有限公司 | Device for preparing drinking water by electrolysis |
| CN105973955A (en) * | 2016-04-26 | 2016-09-28 | 中国科学院电子学研究所 | Tin-palladium composite electrode and preparation method and application thereof |
| CN107739075A (en) * | 2017-11-02 | 2018-02-27 | 广西大学 | A kind of method of the electro-catalysis of organic pollutant wastewater containing chloro reduction dechlorination |
| CN109175347A (en) * | 2018-08-31 | 2019-01-11 | 中国科学院福建物质结构研究所 | A kind of Au-Ir Nanoalloy, preparation method and the application as catalyst |
| CN114011251A (en) * | 2021-12-22 | 2022-02-08 | 南京水滴智能环保装备研究院有限公司 | Conductive film for efficiently removing nitrate in water and preparation method thereof |
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2002
- 2002-12-13 CN CN 02155454 patent/CN1232446C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100432297C (en) * | 2004-12-15 | 2008-11-12 | 中国科学院生态环境研究中心 | Electrode for removing nitrate from water and preparation method thereof |
| CN101346315B (en) * | 2005-10-28 | 2012-06-27 | 阿夸特克股份有限公司 | Highly stable aqueous solution, electrode with nanocoating for preparing the solution and method for making this electrode |
| CN103233242A (en) * | 2013-03-30 | 2013-08-07 | 浙江工业大学 | DSA/Pb alloy composite electrode, its preparation method and application |
| WO2015154713A1 (en) * | 2014-04-12 | 2015-10-15 | 大连双迪创新科技研究院有限公司 | Device for preparing drinking water by electrolysis |
| US10294128B2 (en) | 2014-04-12 | 2019-05-21 | Dalian Shuangdi Innovative Technology Research Institute Co., Ltd. | Device for preparing drinking water by electrolysis |
| CN104646405A (en) * | 2015-02-15 | 2015-05-27 | 中国科学院生态环境研究中心 | Electrode device and method for lowering arsenic and lead concentrations in rice |
| CN105973955A (en) * | 2016-04-26 | 2016-09-28 | 中国科学院电子学研究所 | Tin-palladium composite electrode and preparation method and application thereof |
| CN107739075A (en) * | 2017-11-02 | 2018-02-27 | 广西大学 | A kind of method of the electro-catalysis of organic pollutant wastewater containing chloro reduction dechlorination |
| CN107739075B (en) * | 2017-11-02 | 2021-04-20 | 广西大学 | Electrocatalytic reduction dechlorination method for wastewater containing chlorinated organic pollutants |
| CN109175347A (en) * | 2018-08-31 | 2019-01-11 | 中国科学院福建物质结构研究所 | A kind of Au-Ir Nanoalloy, preparation method and the application as catalyst |
| CN114011251A (en) * | 2021-12-22 | 2022-02-08 | 南京水滴智能环保装备研究院有限公司 | Conductive film for efficiently removing nitrate in water and preparation method thereof |
| CN114011251B (en) * | 2021-12-22 | 2024-01-23 | 南京水滴智能环保装备研究院有限公司 | Conductive film for efficiently removing nitrate in water and preparation method thereof |
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