CN102642955B - Electrochemical removal method for heavy metals in breeding circulating seawater - Google Patents
Electrochemical removal method for heavy metals in breeding circulating seawater Download PDFInfo
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Abstract
The invention discloses an electrochemical removal method for heavy metals in breeding circulating seawater, belonging to the technical field of water treatment. The method comprises the following steps: firstly, adjusting the pH value of seawater to be treated to 1.0-2.4, and removing heavy metals in the seawater by utilizing a three-electrode system in an electrochemical mode; testing the concentration of the surplus heavy metals in the treated seawater by utilizing the three-electrode system in an anodic stripping voltammetry mode; representing the removal effect; and finally, adjusting the pH value of the seawater which is completely treated by adding sodium hydroxide, and adjusting the pH value by adding fresh water to the salinity required for actual breeding. The method is high in application current efficiency and low in material consumption and running cost, and is simple to operate and easy to learn without special training; and moreover, work electrodes are less vulnerable to poisoning, namely, the work electrodes are not be polluted. Five kinds of heavy metals in the seawater can be simultaneously removed efficiency and rapidly. The heavy metal removal effects of the method can be represented by only one piece of equipment without any other auxiliary materials or conditions.
Description
Technical field:
The invention belongs to water-treatment technology field, relate to particularly a kind of electrochemistry removal method that cultivates heavy metal copper in circulating seawer, zinc, lead, mercury, cadmium.
Background technology:
Earlier 2000s, fish production be in by fish for cultivation, by output to the quality transitional period, efficient, the intensive aquaculture of China enters the fast track of development.Industrial circulating water cultivating is compared with traditional breeding way, have water saving, save land, high-density is intensive, without seasonal effect with discharge controlled characteristics, meet the requirement of Sustainable development, be the inexorable trend that following aquaculture mode changes.Due to the aquaculture water resource circulation utilization, in this technology, one of key element is ACTIVE CONTROL water quality.Up to now, many technology (comprising settling tank, sandfiltration pot, sieve-bend screen, foam separation, ozonization plant, ultraviolet disinfector, biological filter, liquid oxygen oxygenation, artificial swamp etc.) based on physics, chemistry and biological principle are applied to cultivating circulating water treatment, and nutritive salt, chemical oxygen demand (COD) (COD), medicine in reuse water is residual to accurately controlling, waste etc.Yet, have research to show that clearly the existence of Heavy Metals in Waters not only can affect the growth of hydrocoles, and be difficult for being biodegradable.In addition, heavy metal is accumulated in vivo and can significantly be reduced the fishery products quality, brings the edible safety risk.Future Society certainly will propose more and more higher requirement to the heavy metal content in fishery products to the requirement of high-quality food, and therefore, in breeding environment, the control of heavy metal is also the inevitable requirement that builds Harmless quality of production standards system.Mainly contain following several to the removal method of heavy metal in waste water at present:
Chemical precipitation method (Li Dinglong, Jiang Sheng. the scheme comparative studies of heavy metal containing wastewater treatment. industrial safety and environmental protection, 2005,31 (12), 18-19).Principle is to add chemical substance to react in containing the waste water of heavy metal, makes the heavy metal that is dissolved state change water-fast precipitation compound into and removes.Although technique is simply ripe, needs the chemical reagent amount large, easily causes secondary pollution; The follow-up difficulty that removes of heavy metal.
By Bubble-floating Method (F.Fu, Q.Wang.Removal of heavymetal ions from wastewaters:Areview.Journal of Environmental Management, 2011,92 (3), 407-418.).Utilize the adsorption of bubble that chemical reaction throw out or the clathrate separation of heavy metal are removed, have the advantages that equipment is simple, floor space is little, be suitable for periodical operation, but need equally the chemical reagent of complicated, complex operation is difficult for automatization.
Ion exchange method (F.Fu, Q.Wang.Removal of heavymetal ions from wastewaters:Areview.Journal of Environmental Management, 2011,92 (3), 407-418; D.W.O ' Connell, C.Birkinshaw, T.F.O ' Dwyer.Heavymetal adsorbents prepared from the modification of cellulose:A review.Bioresource Technology, 2008,99 (15), 6709-6724.).Utilize ion-exchanger and heavy metal ions in wastewater generation ion exchange, thereby isolate heavy metal ion.Advantage is that the processing capacity is large, and effluent quality is good, recyclable heavy metal resources, non-secondary pollution.Shortcoming resin vulnerable to pollution or oxidation deactivation, regeneration is frequent, and reaction time is long, and process cost is high.
Membrane separation process (F.Fu, Q.Wang.Removal of heavymetal ions from wastewaters:Areview.Journal of Environmental Management, 2011,92 (3), 407-418; M.A.Barakat, E.Schmidt.Polymer-enhanced ultrafiltration process for heavymetals removal from industrial wastewater.Desalination, 2010,256 (1-3), 90-93.).The specific semi-permeable membrane that utilizes water molecules to see through is held back pollutent, have efficient, without phase transformation, energy-conservation, equipment is simple, easy to operate, do not add the advantage such as chemical reagent, but membrane module is expensive, regeneration is difficult.
Biotechnology method (F.Fu, Q.Wang.Removal of heavymetal ions from wastewaters:Areview.Journal of Environmental Management, 2011,92 (3), 407-418; E.Metaxa, G.Deviller, P.Pagand, C.Alliaume, C.Casellas, J.P.Blancheton.High rate algal pond treatment for water reuse in a marine fish recirculation system:Water purification and fish health.Aquaculture, 2006,252 (1), 92-101; S.Dhote, S.Dixit.Water quality improvement through macrophytes-a review.Environ.Monit.Assess, 2009,152,149-153.).Utilize the physiological property of microorganism or plant materials to process heavy metal wastewater thereby, mainly contain biosorption process, bio-flocculation process and phytoremediation.Have the advantages such as efficient is high, cost is low, secondary pollution is few, but microorganism culturing and domestication time are long, wayward, and mostly selective.
Electrolytic process (P.P.Li, C.S.Peng, F.M.Li, S.X.Song, A.O.Juan.Copper and nickel recovery from electroplating sludge by the process of acid-leaching and electro-depositing.Int.J.Environ.Res., 2011,5 (3), 797-804; Yuan Shaojun, Jiang Bin, Li Tiancheng, Wang Dawei, Li Xingang. electrolytic process purifies the experimental study of heavy metal ion-containing waste water. chemical industry and engineering, 2003,20 (1), 7-10.).Utilize electrode and heavy metal ion generation electrochemical action and eliminate the method for its toxicity, having equipment simple, taking up an area littlely, easy handling can reclaim the advantage of valuable metal.But existing electrolytic process working electrode is expensive and renewal is difficult for, and current efficiency is low.
Though above-mentioned kind of method respectively has characteristics, also be not applicable to the economy of heavy metal in the industrialized culture circulating seawer, the efficient removal at present.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of electrochemistry removal method that cultivates heavy metal in circulating seawer, based on electrochemical deposition (galvanic deposit) principle, adopting the conductive carbon black paste electrode is electrochemical working electrode, disposable removal industrialized culture circulating seawer comprises copper, zinc, lead, mercury and cadmium 5 heavy metal species, the pollution problem that aquaculture product is caused with the heavy metal that solves in the industrialized culture circulating seawer.
The present invention is achieved through the following technical solutions:
A kind of electrochemistry removal method that cultivates heavy metal in circulating seawer comprises the following steps:
1), arrange platinum guaze or glass carbon post electrode, saturated calomel reference electrode and working electrode conductive carbon black paste electrode three-electrode system in cultivation recirculated water water treating pond; Connect three-electrode system and electrochemical workstation, connect the 220V alternating-current;
The method of described conductive carbon black paste electrode preparation is: conductive carbon black and analytical pure wax oil mix with mass ratio 8.5:7.0, compacting in the plastics tubing of then packing into, and afterbody inserts the copper cash conduction;
2), inject the seawater that certain volume is treated removing heavy metals in the circulating water treatment pond, regulate seawater to pH 1.0-2.4 with hydrochloric acid;
3), regulating the electrochemical apparatus working parameter makes the working electrode current potential be-1.5V, beginning heavy deposition metal on working electrode
4) upgrade, according to actual needs working electrode, remove simultaneously the reducing metal layer;
5), utilize Anodic Stripping Voltammetry Determination to process residual gravity metal concentration in seawater, characterize removal effect;
6), determine whether continue electrodeposition process according to characterization result, until reach established standards;
7), add the sodium hydroxide adjustment seawater pH value that is disposed, add the salinity that fresh water is adjusted to actual cultivation needs.
Further, the working electrode arrangement state in described three-electrode system satisfies and to be easy to take out and to upgrade operation, its with to interelectrode distance more than 1m.
The present invention's beneficial effect compared with prior art:
1, present device cheap and simple, level of automation is high, and controllability is strong;
2, the present invention is simple to operate easy to learn, need not Special Training;
3, be used as the conductive carbon black paste electrode electrochemical activity surface-area of working electrode in the present invention large, applied current efficient is high; Physical strength is moderate, is the removable heavy metal that is deposited thereon by simple and mechanical shearing, the while Surface Renewal, thereby be not afraid of poisoning (contaminated), and consumptive material is cheap, and running cost is low;
4, the present invention can remove Copper Sea Waters, zinc, lead, mercury and cadmium 5 heavy metal species, efficient quick simultaneously.
5, the present invention when using the heavy metal of electrochemical method in removing breeding seawater, at first regulates the pH to 1.0-2.4 of seawater, and this acidification is simultaneously to the seawater sterilization and disinfection;
6, heavy metal removal effect of the present invention can adopt anodic stripping voltammetry to characterize by same set of equipment, need not any other subsidiary material and condition.
Description of drawings:
The water treatment system schematic diagram that Fig. 1 the inventive method is used
1, electrochemical workstation 2, working electrode 3, reference electrode 4, to electrode 5, rising pipe 6, water inlet pipe 7, circulating water treatment pond
Embodiment:
Be described in detail by reference to the accompanying drawings technological method of the present invention below by embodiment, the present embodiment is not done any type of restriction to content of the present invention.
The system that in the cultivation circulating seawer, the electrochemistry removal method of heavy metal is used as shown in Figure 1, the electrochemical treatment system that is comprised of electrochemical workstation 1 and three-electrode system, three parts of recirculated water heavy metal treating pond 7 (electrolyzer) and Inlet and outlet water Controlling System form, and wherein three-electrode system comprises working electrode 2, reference electrode 3 and to electrode 4.
A kind of electrochemistry removal method that cultivates heavy metal in circulating seawer, and automatically realize the sign purpose of heavy metal removal effect, concrete steps are as follows:
1, arrange that in circulating water treatment pond (electrolyzer) platinum guaze or glass carbon post are to the utmost point and saturated calomel reference electrode, take the conductive carbon black paste electrode as working electrode.In three-electrode system, laying of working electrode preferably is convenient to take out renewal; Connect three-electrode system and electrochemical workstation, connect the 220V alternating-current;
2, inject the seawater that certain volume is treated removing heavy metals in the circulating water treatment pond, add fixed (obtaining by calculating) volume hydrochloric acid to regulate seawater to pH 1.0-2.4;
3, regulate the electrochemical apparatus working parameter and make the working electrode current potential be-1.5V, beginning heavy deposition metal on working electrode;
4, upgrade according to actual needs working electrode (mechanical or manual), remove simultaneously the reducing metal layer;
5, utilize Anodic Stripping Voltammetry Determination to process residual gravity metal concentration in seawater, characterize removal effect;
6, determine whether continue electrodeposition process according to characterization result, until reach established standards;
7, add the sodium hydroxide adjustment seawater pH value that is disposed, add the salinity that fresh water is adjusted to actual cultivation needs;
8, water outlet from treating pond enters next cultivation and recycles.
Embodiment
The present embodiment is further explained technology contents of the present invention with turbot industrialized culture recirculated water heavy metal Transformatin.
The electrochemistry removal method of heavy metal in the cultivation circulating seawer specifically comprises the following steps:
Step 1, structure 110m
3Glass reinforced plastic treating pond 7 (containing the inlet/outlet valve door facilities), settle three-electrode system in treating pond---conductive carbon black paste electrode 2 area 1m
2, column glass carbon is to electrode 4 (model: AHDCL; Diameter 2cm, working length 0.8m; Tianjin Aidahengsheng Technology Development Co., Ltd) and 217 type saturated calomel reference electrode 3 (magnetic is got in Shanghai).Working electrode arrangement state satisfies and to be easy to take out and to upgrade operation, its with interelectrode distance is preferably in 1m more than.Special requirement are not done in the reference electrode position.Be equipped with the above 220V of 200W power and exchange (civil power) power supply, adopt CHI660D electrochemical workstation 1 (Shanghai occasion China) to remove and the Characterization result control unit as heavy metal.
Described conductive carbon black paste electrode preparation: conductive carbon black (model HG-1P, the photochemical factory of Shandong Zibo China) with paraffin oil (analytical pure, Tianjin extensively becomes chemical reagent company limited) mix at 8.5: 7.0 with mass ratio, then the compacting in the PVC plastics tubing of diameter 0.56m, wall thickness 2mm of packing into, afterbody inserts the copper cash conduction.
Step 2, by water inlet pipe 6 to the interior injection seawater for the treatment of pond 7 100m
3, add concentrated hydrochloric acid (density 1.19kg/L, massfraction 38%, amount of substance concentration 12mol/L) 2.6L (closing amount of substance 31.2mol), processed water body acidity adjustment to pH 2.0, is made the target heavy metal ion, so that galvanic deposit.Heavy metal in can seawater in pH 1.0-2.4 scope reaches identical ionising treatment effect.
Step 3, electrochemical workstation galvanic deposit operating voltage is set is-1.5V, beginning copper electrowinning, zinc, lead, mercury and cadmium five heavy metal species; Upgrade electrode every the thick working electrode of the 1mm top layer of pruning approximately, about 30min.
Step 4, setting anodic stripping voltammetry are measured the heavy metal working parameter and are :-1.5V electroreduction 5min;-1.5 to 0V sweep fast differentiated pulse volt-ampere scanning with 0.05V/s.Without copper, zinc, lead, mercury and cadmium stripping peak, show that removing purpose reaches (the heavy metal residual concentration is lower than detectability), otherwise continue galvanic deposit on curve.
Step 5, add 31.2mol sodium hydroxide (1.248kg) in removal heavy metal seawater up to standard, acidity is recalled to former pH value.Also can change as required and add amount of sodium hydroxide, pH is transferred to preset value.If necessary, add fresh water to regulate salinity to cultivating actual needs value (the reagent salinity that consideration adds).
Step 6, the seawater handled well is discharged by water shoot 5, enter next cultivation circulation.
Be to form the loop with by electric current with working electrode to the effect of electrode, generally select the stable electro-conductive materials (noble electrode) such as glass carbon, platinum, therefore use platinum guaze as playing same effect to electrode in three-electrode system.
Claims (2)
1. electrochemistry removal method that cultivates heavy metal in circulating seawer is characterized in that comprising the following steps:
1), arrange platinum guaze or glass carbon post electrode, saturated calomel reference electrode and working electrode conductive carbon black paste electrode three-electrode system in cultivation recirculated water water treating pond; Connect three-electrode system and electrochemical workstation, connect the 220V alternating-current;
The preparation method of described conductive carbon black paste electrode preparation is: conductive carbon black and analytical pure wax oil mix with mass ratio 8.5:7.0, compacting in the plastics tubing of then packing into, and afterbody inserts the copper cash conduction;
2), inject the seawater that certain volume is treated removing heavy metals in cultivation recirculated water water treating pond, regulate seawater to pH1.0-2.4 with hydrochloric acid;
3), regulating the electrochemical apparatus working parameter makes the working electrode current potential be-1.5V, beginning heavy deposition metal on working electrode;
4) upgrade, according to actual needs working electrode, remove simultaneously the reducing metal layer;
5), utilize Anodic Stripping Voltammetry Determination to process residual gravity metal concentration in seawater, characterize removal effect;
6), determine whether continue electrodeposition process according to characterization result, until reach established standards;
7), add the sodium hydroxide adjustment seawater pH value that is disposed, add the salinity that fresh water is adjusted to actual cultivation needs.
2. a kind of electrochemistry removal method that cultivates heavy metal in circulating seawer according to claim 1 is characterized in that working electrode arrangement state in described three-electrode system satisfies be easy to take out and upgrade operation, its with to interelectrode distance more than 1m.
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| CN102798657B (en) * | 2012-09-04 | 2014-07-02 | 中国水产科学研究院黄海水产研究所 | Site fast detection method for copper, zinc, lead and cadmium as heavy metals in seawater |
| CN103663803A (en) * | 2012-09-17 | 2014-03-26 | 武汉环材科技有限公司 | Efficient electro-deposited heavy metal cleaning system |
| CN103351040B (en) * | 2013-08-01 | 2015-01-21 | 中国水产科学研究院黄海水产研究所 | Removing apparatus and removing method for inorganic arsenic in aquaculture underground seawater |
| CN103626265A (en) * | 2013-11-07 | 2014-03-12 | 太原师范学院 | Method for performing electrocatalytic oxidation on pyrocatechol |
| CN105304914B (en) * | 2015-11-10 | 2017-12-26 | 华东理工大学 | Power extraction method and apparatus in high-concentration heavy metal waste water processing procedure |
| CN107720891A (en) * | 2017-11-21 | 2018-02-23 | 中国石油大学(华东) | A kind of method for promoting the reduction of heavy metal chromium ion electrochemical |
| CN113092564A (en) * | 2019-12-23 | 2021-07-09 | 上海雄图生物科技有限公司 | Method for rapidly detecting heavy metals in water |
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| CN2075422U (en) * | 1989-12-23 | 1991-04-24 | 林春恩 | Water quality improving device for cultivating tank |
| CN101074941A (en) * | 2007-06-21 | 2007-11-21 | 中国科学院长春应用化学研究所 | Method for producing carbon magma bismuth membrane electrode |
| CN101186376A (en) * | 2007-12-18 | 2008-05-28 | 苏州大学 | Method for removing semimetal antimony ion from waste water |
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| JP2006000792A (en) * | 2004-06-18 | 2006-01-05 | Ebara Corp | Apparatus and method for electrodeposition treatment |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2075422U (en) * | 1989-12-23 | 1991-04-24 | 林春恩 | Water quality improving device for cultivating tank |
| CN101074941A (en) * | 2007-06-21 | 2007-11-21 | 中国科学院长春应用化学研究所 | Method for producing carbon magma bismuth membrane electrode |
| CN101186376A (en) * | 2007-12-18 | 2008-05-28 | 苏州大学 | Method for removing semimetal antimony ion from waste water |
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| JP特开2006-792A 2006.01.05 |
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