CN1623699A - Complex strengthen process for removing copper pollution in red soil - Google Patents
Complex strengthen process for removing copper pollution in red soil Download PDFInfo
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- CN1623699A CN1623699A CN 200310106531 CN200310106531A CN1623699A CN 1623699 A CN1623699 A CN 1623699A CN 200310106531 CN200310106531 CN 200310106531 CN 200310106531 A CN200310106531 A CN 200310106531A CN 1623699 A CN1623699 A CN 1623699A
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Abstract
A method for removing the copper pollution in laterite includes such steps as arranging the electrolytic pools at both ends of the polluted laterite region, arranging a processing pool close to each electrolytic pool in order to exchange liquid, inserting electrodes in said electrolytic pools, applying a DC power supply across them, and using an automatic pH control system to control the pH value of cathode pool to be in a certain range.
Description
Technical field
The invention belongs to environmental protection technical field; relate to a kind of composite strengthening method that copper pollutes in the red soil of removing; specifically; be particularly related to and a kind of Electrokinetic Remediation of Polluted Soils technology and chemical complexing abductive approach combined; and pass through control cathode pond acidity accurately and effectively, effectively remove the composite strengthening method that pollutes copper in the red soil.
Background technology
The contaminated soil reparation is current a special kind of skill of needing development badly, because the soil pollution meeting causes very serious environmental problem, influences human health and social development.At present, the soil remediation technology includes chemical reparation, phytoremediation and microorganism reparation etc., though they each have the characteristics of oneself, part also comes with some shortcomings.And carry out multiple recovery technique compound is the new focus of current soil reparation research.
As one of chemical repair method, electric repairing technique is a kind of cleaning, contaminated soil treatment technology efficiently, and it is to add dc source at the contaminated soil two ends, makes the pollutant in the soil move out of soil under electric field action.Because this method is a kind of in-situ processing method, so need not excavate the soil body, reduces expenses; Handle the degree of depth simultaneously and can reach 10-20 rice, treatment effeciency is high; And be applicable to and caused very big attention in developed countries such as the U.S., Germany, Japan in recent years by polytype contaminated soils such as heavy metal and organic pollution.
But, because in electronic repair process process, catholyte will produce OH
-, cause being alkalescence near near the soil the negative electrode, make heavy metal ion be deposited in this regional soil, can not go out the soil body by effective mobility, thereby reduce the treatment effeciency of heavy metal in soil.And in processing procedure, come the pH value of control cathode liquid by add acid solution frequently in catholyte, though can improve treatment effect, this method can not guarantee that the pH of catholyte is fixed on a value, also a large amount of simultaneously labor intensive material resources are so have certain limitation.
The mobility of pollutant in soil is the key factor of its repairing effect of decision.It is to apply chelating agent in soil that chemical complexing is induced, by chemical induction release etc., make pollutant in soil be easy to move, but also lack the method for from soil, removing these complex compounds effectively at present, and adopt washing will expend a large amount of clean water, and cause secondary pollution easily.
U.S. Patent number US 6193867, the day for announcing is February 27 calendar year 2001, name is called flow and the direction to the EOF in the electronic reparation that disclose Hitchens G Duncan invention in the patent of " Managementof soil conditions and electroosmotic flow in electrokineticremediation-controlling electroosmotic flow through porous mediumby applying electric field between plurality of electrodes positionedin porous medium; supplying acid solution to one of electrodes and/orsoil, and supplying a zeta potential " and controls a kind of reinforcement technique.This technology thinks that adding acid treatment is a kind of method of controlling EOF flow and direction, but this processing method does not relate to for the beneficial effect of removing the heavy metal pollution in the soil, and when electronic repairing heavy metal pollution, heavy metal ion shifts out from soil under electric field action mainly based on electromigration, but not EOF, thereby this invention does not solve the efficiency that heavy metal moves out of soil.
Korean patent No. 10-1999-0014523, name is called the reinforcement technique of the employing complexing agent that discloses inventions such as Kim in the patent of " Removal of toxic heavy metalsfrom wastewater sludge using electrokinetic processes ", mentioned in this technology and adopted complexing agent to improve the method for handling the efficient of heavy metal in the mud, but this technology does not relate to the effect when adopting complexing agent to handle the heavy metal in soil pollution, does not emphasize the control of pH yet.
Red soil is a kind of variable charge soils, in China bigger distribution area is arranged.And red soil itself is acid because cation exchange capacity is little, so heavy metal pollution is had very circlet border capacity.At present, the domestic and international report that still lacks at red soil heavy metal pollution recovery technique aspect.And as a kind of variable charge soils, because the character of itself is different from permanent electric charge soil, EOF direction and flow, soil pH and electricity are led etc. obvious change all can be taken place in the electrokinetic process process, so the electronic repair process result on permanent electric charge soil is difficult to directly use on the red soil.Therefore, press for complex technique and the correlation parameters that heavy metal is removed in the research red soil.
Summary of the invention
The object of the present invention is to provide a kind of composite strengthening method that copper pollutes in the red soil of removing, it is the compound recovery technique of polluting at red soil copper, the pH that can realize negative electrode in the electronic repair process controls automatically, has multiple alternative chemical complexing agent, can effectively improve the removal efficient of copper, to overcome existing above-mentioned shortcoming in the prior art.
Above-mentioned purpose of the present invention is achieved in that a kind of composite strengthening method that copper pollutes in the red soil of removing, and it is characterized in that having following steps:
At the contaminated soil two ends electrolytic cell is set respectively, in each electrolytic cell, inserts electrode respectively, and add dc source, so that form the circuit of a closure;
In the other set handling pond respectively of each electrolytic cell, electrolytic cell links to each other with separately treatment pond with conduit and pump respectively, so that carry out fluid exchange;
The acidity that adopts the pH automatic control system to come the control cathode treatment pond makes it to drop in the certain pH range all the time.
The composite strengthening method that copper pollutes in the removal red soil of the present invention, wherein sintered glass is adopted in the isolation of soil and electrolytic cell.
The composite strengthening method that copper pollutes in the removal red soil of the present invention, wherein this electrode is graphite electrode, titanium alloy electrode or platinum electrode.
The composite strengthening method that copper pollutes in the removal red soil of the present invention, wherein the voltage of this dc source is the 20-40 volt.
The composite strengthening method that copper pollutes in the removal red soil of the present invention, wherein this pump is a multi-channel peristaltic pump.
The composite strengthening method that copper pollutes in the removal red soil of the present invention, wherein the pH value in cathode treatment pond is controlled at 3.0-3.5, and the solution composition in the cathode treatment pond is 0.05M Lactic acid solution (transferring pH=3.0 with NaOH) or 0.1M HAc+0.01M NaAc+5mM EDTA.
The composite strengthening method that copper pollutes in the removal red soil of the present invention, wherein this pH automatic control system is made of pHG-2 type Techno-Industrial acidometer, E-201-C type rechargeable type pH combination electrode, temp probe, single channel peristaltic pump.
The composite strengthening method that copper pollutes in the removal red soil of the present invention, wherein this conduit uses the silicone rubber tube of acid-alkali-corrosive-resisting.
The composite strengthening method that copper pollutes in the removal red soil of the present invention, wherein this electrode be shaped as tabular, bar-shaped or netted.
The present invention also provides a kind of electronic repair process device that copper pollutes in the red soil of removing simultaneously, the entire process device is made up of an electronic reparation post, two electrolytic cells, two treatment ponds and soda acid deposit liquid pool, comprises that simultaneously one of dc source, one of multi-channel peristaltic pump, pH automatic control system two covers, sintered glass, electrode, conduit etc. are some.Contaminated soil is filled in electronic reparation post, at its two ends electrolytic cell is set, insert electrode in electrolytic cell, the electrode with dc source connection two ends applies DC voltage, forms the electric-force gradient that runs through soil.The contact position of soil and electrolytic cell isolates with sintered glass, and its effect is to make the polluters such as heavy metal in the soil can pass through electrolytic cell, and prevents that soil particle material etc. from entering under electric field action.Electrolytic cell links to each other with treatment pond by peristaltic pump, ceaselessly and carry out solution exchange between the treatment pond.Pollutant mass-energy in time enters treatment pond from electrolytic cell, is further handled then, separates from solution; Control the acid-base value of electrolyte simultaneously, prevent moving of too high pH value restriction heavy metal in soil ion.The pH automatic control system is made of pH combination electrode, single channel peristaltic pump, Techno-Industrial acidometer among the present invention, the pH combination electrode is linked to each other with the indicator electrode jack at the acidometer back side, the temperature-sensing probe jack of temp probe with its back of the body links to each other, simultaneously the switch of peristaltic pump can link to each other by the interface at the back side on transmitter and the acidometer, by the switch that pickup value on the setting acidometer and release value are controlled peristaltic pump, the in good time acid ﹠ alkali liquid that adds in the electrolysis liquid pool is controlled its pH value.This pH automatic control system can be come the pH of control cathode according to the needs of actual treatment, also controls the pH of anode, or controls the pH of anode and cathode simultaneously with two covers.Electrode material adopts graphite material cheap and easy to get, also can adopt corrosion resistant titanium alloy electrode and platinum electrode, and electrode can be made tabular, bar-shaped or netted as required; Conduit uses the silicone rubber tube of acid-alkali-corrosive-resisting.Above various piece is linked together, by applying DC current, polluter in the soil is brought to the treatment pond that is arranged in the soil two ends by approach such as electromigration, EOF or electrophoresis, thereby and further handle realize contaminated soil subtract dirt or cleaning.
The optimal operating parameter of this technology is:
DC voltage: 20-40V;
Peristaltic pump flow: 12-20ml/min;
Anodic dissolution: water;
The lactic acid of cathode solution: 0.05M (Lactic acid) solution;
In the processing procedure
Control cathode pH value of solution value is 3.0-3.5.
Description of drawings
Fig. 1 is the vertical section organigram of electronic repair process device;
Fig. 2 is the structural representation of cathode treatment pond pH automatic control system;
Fig. 3 is the residual volume of copper in the soil after the electronic reparation.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Experiment red soil picks up from the Jiangxi Yingtan.The red soil of adopting back is air-dry, and levigate its granularity that makes is 0.84mm.This soil is about the cupric sulfate pentahydrate solution mixing of 500mg/kg with copper concentration, holds with the porcelain container then, and adds water and make it be in the waterflooding state, at room temperature cultivates one month, and the red soil after the cultivation is air-dry, sieve, and granularity is 0.25mm, stores for future use.Record the copper concentration of cultivating in the red soil and be about 440mg/kg with chloroazotic acid-perchloric acid cooking method that disappears.
Utilize electronic repair process device shown in Figure 1, with granularity is that the cultivation red soil 1 of 0.25mm is packed in the electronic reparation post 2, between earth pillar and anode electrolysis pond 3, catholyte pond 4, place a sintered glass 9 respectively, flow in anode electrolysis pond 3 and the catholyte pond 4 to stop soil.Electronic reparation post 2 length are 12cm, and diameter is 6.5cm, and whole reparation post can be adorned the red soil of 600g approximately.On electronic reparation post 2, open 11 apertures equidistantly, be used for plugging stainless steel probe 16, be convenient to the voltage drop of each section of earth pillar in the experiments of measuring process.Anode electrolysis pond 3 and catholyte pond 4 are equipped with gas vent, are used for deriving respectively hydrogen and the oxygen that positive and negative the two poles of the earth produce.In anode electrolysis pond 3 and catholyte pond 4, insert electrode 10 respectively, connect D.C. regulated power supply 12, form the circuit of a closure.Electrode material adopts corrosion resistant graphite electrode cheap and easy to get.For the solution in the electrolytic cell can be upgraded, adopt multi-channel peristaltic pump 14 to connect anode electrolysis pond 3 and anode treatment pond 5 respectively, catholyte pond 4 and cathode treatment pond 6 guarantee that electrolyte can recycle.
The acidity that adopts the pH automatic control system to come the control cathode treatment pond makes it to drop in the certain pH range all the time.PH in the treatment pond monitors by pHG-2 type Techno-Industrial acidometer 13.PHG-2 type Techno-Industrial acidometer connects E-201-C type rechargeable type pH combination electrode 11, temp probe 17 and single channel peristaltic pump 15 respectively.The switch of peristaltic pump is controlled by pickup value and the release value set on the acidometer.E-201-C type rechargeable type pH combination electrode and temperature-sensing probe are used for measuring the pH in the treatment pond, feed back to pHG-2 type Techno-Industrial acidometer then.In case the pH that records surpasses the release value of setting, the peristaltic pump that is connected with acidometer is just started working, and discharges in the acid solution and OH
-, the pH value in treatment pond is lower than the pH value of setting on the acidometer, and peristaltic pump just quits work.In addition, in electronic repair process, we add the chemical complexing agent in the catholyte pond, be used for dissolving and release that heavy metal-polluted soil is induced in complexing, thereby improve treatment effect.
With reference to Fig. 2, it is the structural representation of cathode treatment pond pH automatic control system, and the circuit of describing the pH automatic control system in Fig. 2 in detail connects and operation principle.There are some interfaces at the back side 18 of pHG-2 type Techno-Industrial acidometer, and wherein two interfaces of a, b link to each other with 220V AC power 19, supplies with the required power supply of acidometer; Two interfaces of f, g link to each other with transmitter 20, and simultaneously by 220V AC power 19 supply powers, the other end of transmitter 20 links to each other with single channel peristaltic pump 13, the switch of control single channel peristaltic pump 15.E-201-C type rechargeable type pH combination electrode 11 links to each other with the indicator electrode jack 21 at the acidometer back side 18, l, m two interfaces link to each other with reference electrode reference electrode plug 22, and the m interface links to each other with the lead that temperature-sensing probe jack 23 involves and merges into temperature-sensing probe 17 and be inserted in the electrolysis liquid pool 6.Transmitter 20 obtains control signal from pHG-2 type Techno-Industrial acidometer 13 and controls single channel peristaltic pump 15, and that does not stop carries acid solution from acid deposit liquid pool 7 to cathode treatment pond 6, so that control its pH value.
Copper pollution red soil is being carried out in the process of electronic reparation, studied the remediation efficiency under the different experimental conditions, and measure the electrical conductivity of solution in EOF, pH, voltage, electric current and the negative and positive electrolysis liquid pool under the different experimental conditions termly, be used for understanding the mechanism of action of electronic repair process.EOF in the experimentation draws by the Volume Changes of calculating solution in the anode deposit pond.PH directly measures by the accurate pH meter of pHS-3B.Voltage and current is measured with DT9208B type digital multimeter.Electrical conductivity then records with DDS-11A type electric conductivity instrument.After batch processing finishes, the soil in the electronic reparation post evenly is cut into ten equal portions, air-dry, levigate with agate mortar, granularity is 0.25mm, stores for future use.From granularity is take out the 0.25mm pedotheque a small amount of, equally with agate mortar levigate to granularity be 0.149mm, with disappear full copper in the cooking method extraction pedotheque of chloroazotic acid-perchloric acid, be prepared into liquid to be measured.Granularity is pH, the electrical conductivity that the air-dry soil sample of 0.25mm is used for measuring soil.Copper content in the solution is measured with Hitachi 180-80 Atomic Absorption Spectrometer.
In order to obtain best processing parameter, designed the compound repairing test under the different condition, comprise different voltage change, different treatment media etc. respectively.What wherein, experiment 1,2,3,4 was adopted respectively is: deionized water, 0.1M HAc+0.01M NaAc solution, 0.1M HAc+0.01M NaAc+5mM EDTA solution, 0.05M Lactic acid (transferring pH=3.0 with NaOH).Experiment 5,6 at experiment 3,4, has designed the experiment under the different voltages respectively.Experiment shows: the red soil of tool variable charge is suitable for carrying out with the method for electronic reparation the decontamination processing of heavy metal.
Fig. 3 represents is the residual volume of copper in the earth pillar behind the electronic reparation 900h.Can see on scheming: the copper content after the electronic reparation the soil is starkly lower than the copper content before handling.When with Lactic acid+NaOH control cathode pond pH, the clearance of copper is up to more than 80% in the red soil.The clearance of copper also reaches about 50% under all the other conditions.It is a kind of very effective chemical complexing agent that this explanation lactic acid carries out aspect the electronic reparation at the red soil that copper is polluted.
The invention has the beneficial effects as follows: by to applying different DC voltages, use the different chemical complexing agent and handling the research of treatment effects such as acidity, the result shows that the processing of using 0.05M Lactic acid is most effective in the 20-40V removal, reached 80%, use 0.1M HAc+0.01M NaAc+5mM EDTA when voltage 40V, to remove efficient secondly, being 73.11%, is 64.98% and do not use the processing clearance of complexing agent.Concrete experimental result such as following table 1.
Table 1 different disposal is to the treatment effect of copper in the red soil
Total clearance of voltage processing time
Cathode solution is formed
(V) (h) (％)
Test-01 deionized water 20 900 64.98
Test-02 0.1M HAc+0.01M NaAc 20 900 65.44
Test-03 0.1M HAc+0.01M NaAc+5mM EDTA 20 900 49.49
Test-04 0.05M Lactic acid (transferring pH=3.0) 20 900 80.81 with NaOH
Test-05 0.1M HAc+0.01M NaAc+5mM EDTA 40 900 73.11
Test-06 0.05M Lactic acid (transferring pH=3.0) 40 900 81.77 with NaOH
After using the pH automatic control system, guarantee the comparativity between the experimental result on the one hand, also saved manpower on the other hand, improved the accuracy of control.
Claims (9)
1, a kind of composite strengthening method of removing copper pollution in the red soil is characterized in that having following steps:
At the contaminated soil two ends electrolytic cell is set respectively, in each electrolytic cell, inserts electrode respectively, and add dc source, so that form the circuit of a closure;
In the other set handling pond respectively of each electrolytic cell, electrolytic cell links to each other with separately treatment pond with conduit and pump respectively, so that carry out fluid exchange;
The acidity that adopts the pH automatic control system to come the control cathode treatment pond makes it to drop in the certain pH range all the time.
2, the composite strengthening method that copper pollutes in the removal red soil as claimed in claim 1 is characterized in that: sintered glass is adopted in the isolation of soil and electrolytic cell.
3, the composite strengthening method that copper pollutes in the removal red soil as claimed in claim 1, it is characterized in that: described electrode is graphite electrode, titanium alloy electrode or platinum electrode.
4, the composite strengthening method that copper pollutes in the removal red soil as claimed in claim 1, it is characterized in that: the voltage of described dc source is the 20-40 volt.
5, the composite strengthening method that copper pollutes in the removal red soil as claimed in claim 1, it is characterized in that: described pump is a multi-channel peristaltic pump.
6, the composite strengthening method that copper pollutes in the removal red soil as claimed in claim 1, it is characterized in that: the pH value in cathode treatment pond is controlled at 3.0-3.5, and the solution composition in the cathode treatment pond is 0.05MLactic acid solution or 0.1M HAc+0.01M NaAc+5mM EDTA.
7, the composite strengthening method that copper pollutes in the removal red soil as claimed in claim 1, it is characterized in that: described pH automatic control system is made of pHG-2 type Techno-Industrial acidometer, E-201-C type rechargeable type pH combination electrode, temp probe, single channel peristaltic pump.
8, the composite strengthening method that copper pollutes in the removal red soil as claimed in claim 1 is characterized in that: described conduit uses the silicone rubber tube of acid-alkali-corrosive-resisting.
9, the composite strengthening method that copper pollutes in the removal red soil as claimed in claim 3, it is characterized in that: being shaped as of described electrode is tabular, bar-shaped or netted.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429507C (en) * | 2006-04-29 | 2008-10-29 | 南京大学 | Experimental parameter investigating method for electric restoring polluted soil and groundwater |
| CN102513348A (en) * | 2011-12-15 | 2012-06-27 | 中国科学院南京土壤研究所 | Electric complex-strengthening repairing method and device of heavy metal-organic co-contaminated soil |
| CN102527707A (en) * | 2012-02-24 | 2012-07-04 | 上海市环境科学研究院 | Enhanced electrokinetic remediation method of heavy metal contaminated soil |
| CN106513433A (en) * | 2017-01-20 | 2017-03-22 | 中国地质科学院矿产资源研究所 | Electric repair turnover device for heavy metal contaminated soil |
| CN116282577A (en) * | 2023-03-25 | 2023-06-23 | 西安建筑科技大学 | Method for repairing copper-containing wastewater by biomineralization based on pH value regulation and control |
-
2003
- 2003-12-05 CN CN 200310106531 patent/CN1623699A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429507C (en) * | 2006-04-29 | 2008-10-29 | 南京大学 | Experimental parameter investigating method for electric restoring polluted soil and groundwater |
| CN102513348A (en) * | 2011-12-15 | 2012-06-27 | 中国科学院南京土壤研究所 | Electric complex-strengthening repairing method and device of heavy metal-organic co-contaminated soil |
| CN102527707A (en) * | 2012-02-24 | 2012-07-04 | 上海市环境科学研究院 | Enhanced electrokinetic remediation method of heavy metal contaminated soil |
| CN106513433A (en) * | 2017-01-20 | 2017-03-22 | 中国地质科学院矿产资源研究所 | Electric repair turnover device for heavy metal contaminated soil |
| CN116282577A (en) * | 2023-03-25 | 2023-06-23 | 西安建筑科技大学 | Method for repairing copper-containing wastewater by biomineralization based on pH value regulation and control |
| CN116282577B (en) * | 2023-03-25 | 2024-05-28 | 西安建筑科技大学 | Method for repairing copper-containing wastewater by biomineralization based on pH value regulation and control |
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