CN104787860A - Method for treating hexavalent chromium in waste water by utilizing metal semi-fuel cell - Google Patents
Method for treating hexavalent chromium in waste water by utilizing metal semi-fuel cell Download PDFInfo
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- CN104787860A CN104787860A CN201510175576.6A CN201510175576A CN104787860A CN 104787860 A CN104787860 A CN 104787860A CN 201510175576 A CN201510175576 A CN 201510175576A CN 104787860 A CN104787860 A CN 104787860A
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Abstract
The invention provides a method for treating hexavalent chromium in waste water by utilizing a metal semi-fuel cell. A reactor comprises a cathode chamber and an anode chamber which are partitioned by a diaphragm; an anode is arranged in the anode chamber; a cathode is arranged in the cathode chamber; the anode and the cathode are connected with each other through a conducting wire, and are connected with a load to form a closed loop; the anode is made of Zn, Al, Ca, Mg, Li, Fe, or an alloy of Zn, Al, Ca, Mg, Li or Fe; the cathode is made of graphite; the chromium-containing waste water is led into the cathode chamber first, and then seawater or a sodium chloride-containing solution is led into the anode chamber, so that the anode in the anode chamber is dissolved to discharge electrons which are transmitted to the cathode through the conducting wire, and hexavalent chromium is reduced by the electrons into trivalent chromium fast on the surface of the cathode. The method utilizing the metal semi-fuel cell to construct an electrochemical system to treat chromium-containing waste water is an improvement of electrochemical water treatment methods; no additional electrical energy is required; electrical energy can be generated during wastewater treatment, so as to reduce water treatment cost, and achieve trinary benefits in the aspects of the environment, the society and the economy.
Description
Technical field
What the present invention relates to is a kind of process for treating industrial waste water, specifically a kind of method utilizing Metal semi-fuel cells process to contain hexavalent chromium wastewater.
Background technology
Along with industry and economic development, chromium and compound, as the important source material of the industries such as process hides, plating, metallurgy, paint, dyestuff, is used widely.But meanwhile inevitably produce chromate waste water in production process, these pollutents directly enter in environment if not treated, can cause severe contamination to water body, harm ecotope and HUMAN HEALTH.
In waste water, chromium ion mainly exists with the form of Cr (III), Cr (VI), and wherein sexavalent chrome toxicity is very strong, and chromic toxicity is extremely small.Sexavalent chrome has carcinogenic, mutagenic effect to human body, is one of internationally recognized three kinds of carcinogenic metal objects, one of 129 kinds of priority pollutants that Ye Shi Environmental Protection Agency generally acknowledges.Specify in the wastewater discharge standard of China that the concentration of Cr (VI) is 0.5mg/L, total chrome content must not more than 1.5mg/L, and therefore the economical and efficient process of chromate waste water is very important.Domestic and international investigator has carried out a large amount of research work in route for treatment of chromium containing waste water, and current treatment process comprises absorption method, electrochemical process, ion exchange method, membrane separation process and biological process, and various treatment process all has its relative merits.
Because the treatment process of current chromate waste water all exists certain deficiency, thus carry out improving and optimizing on the basis of former treatment process, improve processing efficiency, nontoxicization accelerating chromate waste water processes, and becomes a new research direction.
Electrochemical treatment as waste water is more promising a kind of technology in various treatment process, it is the process utilizing direct current to carry out solution oxide reduction reaction, utilize electrolyzer process waste water, namely in electrolytic process, negative electrode ejected electron, some positively charged ion in waste water is reduced because obtaining electronics, and negative electrode plays reductive agent.Anode obtains electronics, and make some negatively charged ion in waste water oxidized because losing electronics, anode plays oxygenant.Pollutent in waste water carry out respectively at negative and positive the two poles of the earth redox reaction or with the effect of electrode reaction product, be converted into the separated removing of harmless components, poisonous hexavalent chrome reduction is mainly first become the trivalent chromium of low toxicity by the principle of its processing waste water containing chrome, then trivalent chromium precipitation is removed.Though utilize the electrochemical water treating method of electrolyzer process waste water to have the advantages such as process pollutent is in extensive range, processing efficiency is high, secondary pollution is few, it consumes electric energy, and the shortcoming that processing cost is higher limits it and uses on a large scale.
Employing microbiological fuel cell process waste water is study hotspot in recent years, and it produces electric energy while process waste water, reduces the processing cost of waste water, can realize the Sustainable development of sewage disposal to greatest extent.Therefore utilize battery technology process waste water to be undoubtedly the significant innovation of sewage disposal theory at sewage treatment area, have broad application prospects.
Metal semi-fuel cells (MSFC) utilizes metal (magnesium, aluminium etc.) to be anode, is oxygenant, has a kind of energy conversion device of fuel cell and battery characteristics concurrently with hydrogen peroxide or dissolved oxygen.The anode of MSFC has the feature of battery, and namely anode (as Al, Mg etc.) is consumed in battery discharge procedure, and negative electrode has the feature of fuel cell, and namely oxygenant is (as O
2, H
2o
2deng) being transported to negative electrode continuously from outside, negative electrode itself does not consume, and therefore this electrochemical energy converter device between battery and fuel cell is become " partly " fuel cell.It has that specific energy is high, sparking voltage is large and stable, use safety, without ecological pollution and the outstanding advantages such as the mechanical charge time is short.Metal semi-fuel cells has higher output voltage and electric current than microbiological fuel cell, and therefore its speed at the reduction of cathode contamination thing, detoxification is faster, efficiency is higher.
Summary of the invention
The object of the present invention is to provide one need not additional electric energy, while process waste water, produce electric energy, what processing cost was low utilizes chromic method in Metal semi-fuel cells process waste water.
The object of the present invention is achieved like this:
Barrier film is adopted to separate formation reactor between cathode compartment and anolyte compartment, anode is positioned at the inside of anolyte compartment, negative electrode is positioned at the inside of cathode compartment, be connected by wire between anode with negative electrode, and connect to form loop line with load, described anode is zinc, aluminium, calcium, magnesium, lithium, one in iron and alloy thereof, described negative electrode is graphite, first chromate waste water is introduced cathode compartment, the solution of seawater or sodium chloride-containing is introduced anolyte compartment, anolyte compartment's inner anode dissolves ejected electron, negative electrode is delivered to by wire, sexavalent chrome obtains electronics at cathode surface and is reduced into trivalent chromium rapidly.
The present invention can also comprise:
1, be provided with agitator at cathode compartment to stir.
2, the concentration of described sodium chloride solution is 0.7mol/L.
The present invention is using chromyl waste water as the fuel of negative electrode, build the chromyl waste water of Metal semi-fuel cells process, for the electrolyzer of prior art, need not additional electric energy, and electric energy can be produced while process waste water, reducing processing cost, is a promising method.
Technical measure mainly comprises container, anode, negative electrode, described anode is the one in the metals such as zinc, aluminium, calcium, magnesium, lithium, iron and alloy thereof, described negative electrode is the one of the insoluble electrodes such as graphite, described container is reactor i.e. two rooms Metal semi-fuel cells, reactor comprises cathode compartment and anolyte compartment, cathode compartment and lower end, anolyte compartment have water-in respectively, there is water outlet upper end, anode is positioned at the inside of anolyte compartment, negative electrode is positioned at the inside of cathode compartment, two interpolars are connected by copper conductor, and connect to form loop line with load.Adopt barrier film to separate between room, the two poles of the earth, agitator can be provided with at cathode compartment and stir, to ensure the Homogeneous phase mixing of solution and efficient electrogenesis.
Metal semi-fuel cells process is first chromate waste water is introduced cathode compartment containing the method for the trade effluents such as sexavalent chrome, the solution of seawater or sodium chloride-containing is introduced anolyte compartment, anolyte compartment's inner anode dissolves ejected electron, negative electrode is delivered to by wire, poisonous sexavalent chrome obtains electronics at cathode surface and is reduced into rapidly the trivalent chromium of low toxicity, reaches detoxification object.
In addition, the present invention is in the process of processing waste water containing chrome, and the electronics that anode autolysis produces is delivered to negative electrode by external circuit, at cathode surface reduction of hexavalent chromium.Not only do not need additional electric energy but also create electric energy simultaneously, greatly reducing processing cost like this.
The present invention utilizes Metal semi-fuel cells processing waste water containing chrome to have better effect than the current microbiological fuel cell processing waste water containing chrome that utilizes, reason is that the open circuit potential of anode is more negative, whole processing system of battery is made to produce higher output voltage, larger reaction current, thus improves the water treatment effect of whole system.Be the sexavalent chrome of 18mg/L with process initial concentration of the present invention, after process 80min, clearance can reach about 82%, have treatment effect better, the advantage such as stable effluent quality, processing cost be low, have broad application prospects.
It is a change to electrochemical water treating method that the present invention utilizes Metal semi-fuel cells to build electro-chemical systems processing waste water containing chrome, do not need additional electric energy, and electric energy can be produced while wastewater treatment, thus reduce cost of water treatment, there is the triple benefit of environment, society and economy.
The present invention not only can processing waste water containing chrome, also be applicable to the pollutant removal (as denitrogenation, dechlorination, Azo dye decol, oil of mirbane conversion and uranium conversion etc.) in other water with oxidizing property, can be electric energy by chemical energy effectively, obtain good water treatment effect simultaneously.
In the present invention, battery configuration adopts two rooms Metal semi-fuel cells, and structure is simple, is easy to combination, expands treatment scale, is easy to change operational condition, is conducive to the optimization of battery.
Accompanying drawing explanation
Fig. 1 is the structural representation of battery of the present invention;
Fig. 2 is the treatment effect of Metal semi-fuel cells operating period chromate waste water of the present invention;
Fig. 3 is the synchronous electrogenesis performance of Metal semi-fuel cells of the present invention when processing waste water.
Embodiment
Below in conjunction with accompanying drawing citing, the present invention is described in more detail:
Composition graphs 1, reactor composition of the present invention comprises anolyte compartment 1 and cathode compartment 2, is separated between room, the two poles of the earth by barrier film 3, and two electrodes are placed in anolyte compartment 1 respectively and cathode compartment 2 is inner, and anode material 4 adopts aluminium sheet, and negative electrode 5 adopts graphite cake.The anolyte compartment of two rooms reactor and cathode compartment lower end and upper end are respectively equipped with water-in 6,8 and water outlet 7,9, cathode compartment adopts magnetic agitation, two interpolars are connected by copper conductor, and connect to form loop line with load 10, computer 11, and the regulation range of load is 1 ~ 10000 Ω.
When reactor runs, chromate waste water enters cathode compartment 2 by cathode compartment water-in 8, intermittent operation, at interval of 20min sampling analysis cathode compartment hexavalent chromium concentration, investigates chromic removal effect.The NaCl solution of 0.7mol/L adds anolyte compartment, and dissolve ejected electron at anolyte compartment's metal anode, be then delivered to negative electrode by external circuit, sexavalent chrome poisonous on negative electrode obtains the trivalent chromium that electronics is reduced into low toxicity, reaches the effect of detoxification.Because reactor of the present invention is exactly Metal semi-fuel cells, therefore can produce electric energy when synchronous processing waste water, reduce the processing cost of waste water.
Test-results is as follows:
Fig. 2 is the treatment effect of Metal semi-fuel cells steady operation period chromate waste water of the present invention.As shown in Figure 2, hexavalent chromium-treatments concentration is 18mg/L, and when operation 20,80min, chromic clearance is respectively 51.1% and 82.4%, has good removal effect.
Fig. 3 is Metal semi-fuel cells synchronous electrogenesis performance when processing waste water containing chrome that the present invention builds.Powertrace is measured by the contact resistance changing external circuit.As shown in Figure 3, the peak power output of Metal semi-fuel cells is 23.5W/m
3.
Therefore, the invention provides a kind of novel method utilizing Metal semi-fuel cells processing waste water containing chrome.It is low that this method has processing cost, and the synchronous advantage producing electric energy, is with a wide range of applications in actual applications.
Claims (3)
1. one kind utilizes chromic method in Metal semi-fuel cells process waste water, it is characterized in that: between cathode compartment and anolyte compartment, adopt barrier film to separate formation reactor, anode is positioned at the inside of anolyte compartment, negative electrode is positioned at the inside of cathode compartment, be connected by wire between anode with negative electrode, and connect to form loop line with load, described anode is zinc, aluminium, calcium, magnesium, lithium, one in iron and alloy thereof, described negative electrode is graphite, first chromate waste water is introduced cathode compartment, the solution of seawater or sodium chloride-containing is introduced anolyte compartment, anolyte compartment's inner anode dissolves ejected electron, negative electrode is delivered to by wire, sexavalent chrome obtains electronics at cathode surface and is reduced into trivalent chromium rapidly.
2. according to claim 1ly utilize chromic method in Metal semi-fuel cells process waste water, it is characterized in that: be provided with agitator at cathode compartment and stir.
3. according to claim 1 and 2ly utilize chromic method in Metal semi-fuel cells process waste water, it is characterized in that: the concentration of described sodium chloride solution is 0.7mol/L.
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| CN201510175576.6A CN104787860B (en) | 2015-04-14 | 2015-04-14 | One utilizes Metal semi-fuel cells to process chromic method in waste water |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217800A (en) * | 2015-08-25 | 2016-01-06 | 南京工业大学 | A kind of Graphene/polypyrrole bioelectrode and preparation method thereof and application |
| CN105776434A (en) * | 2016-05-12 | 2016-07-20 | 苏州荣能环保科技有限公司 | Device for separating metal cations from sewage |
| CN106430433A (en) * | 2016-09-09 | 2017-02-22 | 沈阳工业大学 | Internal circulation type electrochemical organic wastewater treatment device |
| CN107892363A (en) * | 2017-12-18 | 2018-04-10 | 清华大学 | The water treatment facilities and method of a kind of synchronous electrogenesis and conversion high volence metal ion |
| CN109001270A (en) * | 2018-10-08 | 2018-12-14 | 兰州大学 | A kind of prior-warning device for hexavalent chromium concentration in industrial wastewater |
| CN110085895A (en) * | 2019-04-12 | 2019-08-02 | 华南师范大学 | A kind of fluid cell and the method using its economic benefits and social benefits processing heavy metal ions in wastewater and organic dyestuff |
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| MX2007013111A (en) * | 2007-10-19 | 2009-04-20 | Univ Guanajuato | Solar energy-assisted process for treating effluents polluted with hexavalent chromium. |
| CN102887559A (en) * | 2011-07-21 | 2013-01-23 | 中国科学院生态环境研究中心 | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater |
| CN103378361A (en) * | 2012-04-20 | 2013-10-30 | 尹华文 | Composite-electrode fuel cell |
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2015
- 2015-04-14 CN CN201510175576.6A patent/CN104787860B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| MX2007013111A (en) * | 2007-10-19 | 2009-04-20 | Univ Guanajuato | Solar energy-assisted process for treating effluents polluted with hexavalent chromium. |
| CN102887559A (en) * | 2011-07-21 | 2013-01-23 | 中国科学院生态环境研究中心 | Electrochemical reduction assistance-based biosorption integrated reactor and treatment method of hexavalent chromium-containing wastewater |
| CN103378361A (en) * | 2012-04-20 | 2013-10-30 | 尹华文 | Composite-electrode fuel cell |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217800A (en) * | 2015-08-25 | 2016-01-06 | 南京工业大学 | A kind of Graphene/polypyrrole bioelectrode and preparation method thereof and application |
| CN105776434A (en) * | 2016-05-12 | 2016-07-20 | 苏州荣能环保科技有限公司 | Device for separating metal cations from sewage |
| CN106430433A (en) * | 2016-09-09 | 2017-02-22 | 沈阳工业大学 | Internal circulation type electrochemical organic wastewater treatment device |
| CN106430433B (en) * | 2016-09-09 | 2022-12-13 | 沈阳工业大学 | Internal circulation type electrochemical organic waste water treatment device |
| CN107892363A (en) * | 2017-12-18 | 2018-04-10 | 清华大学 | The water treatment facilities and method of a kind of synchronous electrogenesis and conversion high volence metal ion |
| CN107892363B (en) * | 2017-12-18 | 2020-07-24 | 清华大学 | Water treatment device and method for synchronously generating electricity and converting high-valence metal ions |
| CN109001270A (en) * | 2018-10-08 | 2018-12-14 | 兰州大学 | A kind of prior-warning device for hexavalent chromium concentration in industrial wastewater |
| CN110085895A (en) * | 2019-04-12 | 2019-08-02 | 华南师范大学 | A kind of fluid cell and the method using its economic benefits and social benefits processing heavy metal ions in wastewater and organic dyestuff |
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