CN104959378A - Bipolar-membrane electrolytic tank capable of removing heavy metal cations in soil - Google Patents
Bipolar-membrane electrolytic tank capable of removing heavy metal cations in soil Download PDFInfo
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- CN104959378A CN104959378A CN201510444768.2A CN201510444768A CN104959378A CN 104959378 A CN104959378 A CN 104959378A CN 201510444768 A CN201510444768 A CN 201510444768A CN 104959378 A CN104959378 A CN 104959378A
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- soil
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- membrane
- anode
- heavy metal
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- 239000002689 soil Substances 0.000 title claims abstract description 86
- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 38
- 150000001768 cations Chemical class 0.000 title abstract description 14
- 238000005341 cation exchange Methods 0.000 claims abstract description 11
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract 1
- 230000005593 dissociations Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000005684 electric field Effects 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000005685 electric field effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 231100000749 chronicity Toxicity 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of environmental pollution treatment equipment and in particular relates to a bipolar-membrane electrolytic tank capable of removing heavy metal cations in soil. The bipolar-membrane electrolytic tank is characterized in that a plurality of soil treatment units, each of which is composed of a bipolar membrane and a cation-exchange membrane, are arranged between an anode and an anion-exchange membrane, and then the electrolytic tank is divided into an anode chamber, a soil treatment chamber, a water chamber and a cathode chamber, and the soil treatment chamber is arranged between the anode and the anion-exchange membrane. The electrolytic tank does not need additional acid, and therefore, the cost can be saved; the heavy metal cations can react with the oxide ions generated by virtue of water dissociation and then precipitated to be removed; a plurality of electrolytic tanks can be connected in series, and a plurality of soil treatment chambers can be treated by use of a pair of negative and positive electrodes; as a result, the current efficiency and the electrolytic tank space utilization rate can be increased, and the energy consumption and the cost can be reduced.
Description
Technical field
The present invention relates to a kind of environmental pollution improvement equipment technical field, particularly one can remove the cationic bipolar membrane electrolytic cell of heavy metal in soil.
Background technology
The thorny environmental problem that heavy metal pollution of soil has become global owing to having disguise, chronicity and irreversibility.China's heavy metal pollution cultivated area about has 2500hm
2, cause grain drop in production more than 1,000 ten thousand tons every year, pollute more than 1,200 ten thousand tons, grain, economic loss more than 200 hundred million yuan.The U.S.'s " immigrant and refugee study " journals report, from content of beary metal such as lead, cadmium, mercury in China's Mainland immigrant blood higher than the immigrant of other areas, wherein lead exceeds 44%.The improvement of heavy metal contaminated soil, more and more attracts widespread attention now, and for this reason, numerous Test And Research Works has been carried out in countries in the world.
At present, the method of domestic and international process heavy metal pollution of soil mainly contains: 1) soil moved in improve the original method: by uncontamination soil displacement contaminated soil, the method needs a large amount of human and material resources and financial resources, and soil restoration needs the long period, and the soil cemented out exists secondary pollution problem.2) elution method: generally use sour drip washing, need a large amount of acid solutions, thus a large amount of sewage can be produced, and easily cause the pollution of underground water.3) electronic chemical method: heavy metal, under DC Electric Field, migrates to ate electrode, then removed by other method, energy consumption is larger.4) phytoremediation: plant is little, processing speed is slow, and plant tall and big heavy metal tolerance is poor.5) microorganism remediation method: timeliness is slow, condition of culture is harsh, and microorganism difficulty survives.Monotechnics has its limitation, cannot be promoted in actual applications.
Bipolar Membrane is a kind of novel ion-exchange composite membranes, utilize the soil of Bipolar membrane water splitting repairing heavy metal pollution, there is current efficiency and electric slot space utilization rate is high, electrode surface side reaction is few, energy consumption is low, without the need to additional a large amount of acid solution, do not produce the advantages such as secondary pollution.It is that Bipolar Membrane is under DC electric field effect that Bipolar membrane water splitting removes the cationic general principle of heavy metal in soil, in intermediate layer, water dissociates, (event is without the need to outer acid supplemented solution to generate hydrogen ion continually, large amount of sewage can not be produced), hydrogen ion to enter in soil chamber the heavy metal cation wash-out in soil out through the anode membrane layer of Bipolar Membrane, by wash-out heavy metal cation out under electric field action, enter hydroecium.Simultaneously, the hydroxide ion (hydroxide ion is produced by negative electrode when single soil chamber) that Bipolar Membrane intermediate layer water decomposition produces, hydroecium is entered through Bipolar Membrane cavity block layer under electric field action, react with the heavy metal cation entering hydroecium, produce precipitation and remove, thus not causing secondary pollution.Heavy metal cation is easy to wash-out, migration and removing from soil under hydrogen ion wash-out and electric field action.The method that applying double pole membrane technology removes heavy metal in soil is organically combined sour drip washing and electronic chemical method, and both's advantage, overcomes its shortcoming.The present invention also can be used for the removal aspect of metal cation in the solid waste such as mud, slag.
Summary of the invention
The invention provides the one cationic bipolar membrane electrolytic cell of applying double pole membrane technology removal heavy metal in soil safely and effectively.This electrolytic cell utilizes Bipolar membrane water splitting, sour elution method and electronic chemical method is combined, and remove heavy metal in soil cation, the heavy metal-polluted soil cations after process significantly reduces, and does not produce secondary pollution.
Bipolar membrane electrolytic cell involved in the present invention, for cuboid channel-shaped structure, formed by anode, anion-exchange membrane and negative electrode sequential in electrolytic cell, and be naturally divided into anode chamber and cathode chamber, anode and negative electrode are connected with the positive and negative polarities of dc source respectively, it is characterized in that between anode and anion-exchange membrane, be provided with multiple soil treatment unit be made up of Bipolar Membrane and cation-exchange membrane, thus electrolytic cell being divided into anode chamber, soil treating chamber, hydroecium, cathode chamber, is soil treating chamber between Bipolar Membrane and cation-exchange membrane.
Described Bipolar Membrane is specific ion exchange membrane, and it is by anode membrane layer and the compounded anions and canons composite membrane of cavity block layer.
Described Bipolar Membrane, is also provided with capillary ceramic plate in the side towards soil treating chamber.
Described cation-exchange membrane, is also provided with capillary ceramic plate in the side towards soil treating chamber.
Described multiple soil treatment unit be made up of Bipolar Membrane and cation-exchange membrane, can infinitely individually be in series in theory, consider the factor of supporting cost and Current Voltage, of the present inventionly multiplely refer to 1 ~ 6, formation two ends is anode chamber, cathode chamber, centre be in-line soil treating chamber, hydroecium ... the chamber structure of multiple series connection of soil treating chamber, hydroecium.
Bipolar Membrane in above-mentioned electrolytic cell is under DC electric field effect, in intermediate layer, water dissociates, the hydrogen ion generated enters in soil chamber through Bipolar Membrane anode membrane layer, the heavy metal cation wash-out in soil out, by wash-out heavy metal cation out under electric field action, enter hydroecium, produce with Bipolar Membrane intermediate layer and move to the hydroxide ion that hydroecium and negative electrode produce and react, produce precipitation and remove.
The advantage that the present invention has and good effect are: 1, Bipolar Membrane is under DC electric field effect, and in intermediate layer, water dissociates and produces hydrogen ion, without the need to outer acid adding, have saved cost, reduce the generation of sewage.2, under hydrogen ion wash-out and electric field action, wash-out, migration and removing from soil is easy to by wash-out heavy metal cation out.3, the hydroxide ion that the heavy metal cation entering hydroecium can produce (or negative electrode generation) with water decomposition in Bipolar Membrane intermediate layer reacts, and produces precipitation and removes, not causing secondary pollution.4, can connect, thus improve current efficiency and electric slot space utilization rate, minimizing electrode surface side reaction generation, reduction energy consumption and cost.
Accompanying drawing explanation
Fig. 1 is that one of the present invention can remove the cationic bipolar membrane electrolytic cell structural representation of heavy metal in soil.
Fig. 2 is that the one arranging multiple soil treatment unit of the present invention can remove the cationic bipolar membrane electrolytic cell structural representation of heavy metal in soil.
Detailed description of the invention
For summary of the invention of the present invention, Characteristic can be understood further, hereby by reference to the accompanying drawings, elaborate by way of example.
In Fig. 1: 1 is electrolytic cell; 2 is anodes; 3 is Bipolar Membrane; 4 is capillary ceramic plates; 5 is cation-exchange membranes; 6 is anion-exchange membranes; 7 is negative electrodes; I is anode chamber; II is soil chamber; III is hydroecium; IV is cathode chamber.
In Fig. 1: 1 is electrolytic cell; 2 is anodes; 3 is Bipolar Membrane; 4 is capillary ceramic plates; 5 is cation-exchange membranes; 6 is anion-exchange membranes; 7 is negative electrodes; I is anode chamber; II is soil chamber; III is hydroecium; IV is cathode chamber.
Embodiment 1
A kind of applying double pole membrane technology is as shown in Figure 1 adopted to remove the cationic electrolytic cell of heavy metal in soil, the both sides of soil chamber use Bipolar Membrane and anode membrane respectively, anode chamber and hydroecium are separated, separate with capillary ceramic plate between soil and film in addition, anode and negative electrode are connected with the positive and negative polarities of dc source respectively.
Containing Pb in contaminated soil handled by the present embodiment
2+, Zn
2+, Cu
2+, Cd
2+, Ni
2+, Cr
3+, Cr
6+etc. heavy metal ion, voltage gradient is 1.0V/m, and electrode spacing is 12cm, and system runs 4d continuously.The Na with 0.05mol/L is all added in anode chamber and cathode chamber
2sO
4solution is as electrolyte, and its liquid level is concordant with contaminated soil, and before and after contaminated soil process, content of beary metal is in table 1.
Table 1: content of beary metal (mg/Kg) before and after soil treatment.
| Heavy metal | Pb | Zn | Cd | Cu | Cr | Ni |
| Before process | 2500 | 2500 | 250 | 2000 | 1500 | 1000 |
| After process | 328 | 378 | 18 | 286 | 192 | 132 |
Embodiment 2
A kind of applying double pole membrane technology is as shown in Figure 2 adopted to remove the cationic electrolytic cell of heavy metal in soil, the both sides of soil chamber separate with anode chamber and hydroecium with Bipolar Membrane and anode membrane respectively, separate with capillary ceramic plate between soil and film in addition, 3 soil chamber are alternately connected with 3 hydroeciums.Anode and negative electrode are connected with the positive and negative polarities of dc source respectively.
Containing Pb in contaminated soil handled by the present embodiment
2+, Zn
2+, Cu
2+, Cd
2+, Ni
2+, Cr
3+, Cr
6+etc. heavy metal ion, voltage gradient is 1.0V/m, and electrode spacing is 36cm, and system runs 4d continuously.The Na with 0.05mol/L is all added in anode chamber and cathode chamber
2sO
4solution is as electrolyte, and its liquid level is concordant with contaminated soil, and before and after contaminated soil process, content of beary metal is in table 2
Table 2: content of beary metal mg/Kg before and after soil treatment
Embodiment 3
A kind of applying double pole membrane technology is as shown in Figure 2 adopted to remove the cationic electrolytic cell of heavy metal in soil, the both sides of soil chamber separate with anode chamber and hydroecium with Bipolar Membrane and anode membrane respectively, separate with capillary ceramic plate between soil and film in addition, 3 soil chamber are alternately connected with 3 hydroeciums.Anode and negative electrode are connected with the positive and negative polarities of dc source respectively.
Containing Pb in contaminated soil handled by the present embodiment
2+, Zn
2+, Cu
2+, Cd
2+, Ni
2+, Cr
3+, Cr
6+deng metal ion, voltage gradient is 0.85V/cm, and electrode spacing is 30cm, and system runs 3d continuously.The Na with 0.1mol/L is all added in anode chamber and cathode chamber
2sO
4solution is as electrolyte, and its liquid level is concordant with contaminated soil, and before and after contaminated soil process, content of beary metal is in table 3.
Table 3: content of beary metal mg/Kg before and after soil treatment
Embodiment 4
A kind of applying double pole membrane technology is as shown in Figure 2 adopted to remove the cationic electrolytic cell of heavy metal in soil, the both sides of soil chamber separate with anode chamber and hydroecium with Bipolar Membrane and anode membrane respectively, separate with capillary ceramic plate between soil and film in addition, 3 soil chamber are alternately connected with 3 hydroeciums.Anode and negative electrode are connected with the positive and negative polarities of dc source respectively.
Containing Pb in contaminated soil handled by this experiment
2+, Zn
2+, Cu
2+, Cd
2+, Ni
2+, Cr
3+, Cr
6+deng metal ion, voltage gradient is 1.5V/cm, and electrode spacing is 32cm, and system runs 5d continuously.The Na with 0.5mol/L is all added in anode chamber and cathode chamber
2sO
4solution is as electrolyte, and its liquid level is concordant with contaminated soil, and before and after contaminated soil process, content of beary metal is in table 4.
Table 4: content of beary metal mg/Kg before and after soil treatment
Claims (5)
1. can remove the cationic bipolar membrane electrolytic cell of heavy metal in soil for one kind, for cuboid channel-shaped structure, by anode in electrolytic cell, anion-exchange membrane and negative electrode sequential form, and be naturally divided into anode chamber and cathode chamber, anode and negative electrode are connected with the positive and negative polarities of dc source respectively, it is characterized in that between anode and anion-exchange membrane, be provided with multiple soil treatment unit be made up of Bipolar Membrane and cation-exchange membrane, thus electrolytic cell is divided into anode chamber, soil treating chamber, hydroecium, cathode chamber, it is soil treating chamber between Bipolar Membrane and cation-exchange membrane.
2. one according to claim 1 can remove the cationic bipolar membrane electrolytic cell of heavy metal in soil, it is characterized in that described Bipolar Membrane is specific ion exchange membrane, and it is by anode membrane layer and the compounded yin, yang composite membrane of cavity block layer.
3. one according to claim 1 can remove the cationic bipolar membrane electrolytic cell of heavy metal in soil, it is characterized in that described Bipolar Membrane, is also provided with capillary ceramic plate in the side towards soil treating chamber.
4. one according to claim 1 can remove the cationic bipolar membrane electrolytic cell of heavy metal in soil, it is characterized in that described cation-exchange membrane dividing plate, is also provided with capillary ceramic plate in the side towards soil treating chamber.
5. one according to claim 1 can remove the cationic bipolar membrane electrolytic cell of heavy metal in soil, it is characterized in that described multiple soil treatment unit be made up of Bipolar Membrane and cation-exchange membrane, there is 1 ~ 6, formation two ends is anode chamber, cathode chamber, centre be in-line soil treating chamber, hydroecium ... the chamber structure of multiple series connection of soil treating chamber, hydroecium.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510444768.2A CN104959378B (en) | 2015-07-27 | 2015-07-27 | A kind of bipolar membrane electrolytic cell of removable heavy metal in soil cation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510444768.2A CN104959378B (en) | 2015-07-27 | 2015-07-27 | A kind of bipolar membrane electrolytic cell of removable heavy metal in soil cation |
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| CN104959378A true CN104959378A (en) | 2015-10-07 |
| CN104959378B CN104959378B (en) | 2017-09-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106623398A (en) * | 2016-10-15 | 2017-05-10 | 太原理工大学 | Ferric salt strengthened electrokinetic remediation device for heavy metal pollution in e-waste dismantling place |
| CN111036670A (en) * | 2019-12-21 | 2020-04-21 | 西安中科贝昂环保科技有限公司 | A separation repair structure for soil heavy metal pollution |
| CN113025829A (en) * | 2021-04-26 | 2021-06-25 | 福建师范大学 | Method for treating copper ore smelting waste residues by applying bipolar membrane electrodialysis |
| CN114368864A (en) * | 2021-12-30 | 2022-04-19 | 嘉兴诚毅环保科技有限责任公司 | Industrial sewage treatment device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5248398A (en) * | 1990-11-16 | 1993-09-28 | Macdermid, Incorporated | Process for direct electrolytic regeneration of chloride-based ammoniacal copper etchant bath |
| CN102070288A (en) * | 2010-12-06 | 2011-05-25 | 河海大学 | Device and method used for restoring sludge polluted by heavy metals |
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-
2015
- 2015-07-27 CN CN201510444768.2A patent/CN104959378B/en not_active Expired - Fee Related
Patent Citations (5)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106623398A (en) * | 2016-10-15 | 2017-05-10 | 太原理工大学 | Ferric salt strengthened electrokinetic remediation device for heavy metal pollution in e-waste dismantling place |
| CN111036670A (en) * | 2019-12-21 | 2020-04-21 | 西安中科贝昂环保科技有限公司 | A separation repair structure for soil heavy metal pollution |
| CN113025829A (en) * | 2021-04-26 | 2021-06-25 | 福建师范大学 | Method for treating copper ore smelting waste residues by applying bipolar membrane electrodialysis |
| CN114368864A (en) * | 2021-12-30 | 2022-04-19 | 嘉兴诚毅环保科技有限责任公司 | Industrial sewage treatment device |
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| Publication number | Publication date |
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| CN104959378B (en) | 2017-09-29 |
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