CN109731905B - Autonomous controllable electric acidification dissociation device and method for soil or substrate sludge pollutants - Google Patents
Autonomous controllable electric acidification dissociation device and method for soil or substrate sludge pollutants Download PDFInfo
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Abstract
The invention provides an autonomous controllable electric acidification dissociation device and method for soil or substrate pollutants, wherein an ion exchange membrane is additionally arranged on one side of a cathode of an electric restoration device to prevent OH ‑ generated by cathode electrolysis from migrating. Under the action of an electric field, H + generated by anodic electrolysis migrates to a cathode, OH ‑ generated by the cathode is isolated by an ion exchange membrane and is accumulated on the inner side of the ion exchange membrane, so that the H + cannot migrate to the anode under the action of the electric field, and the H + is prevented from contacting and carrying out neutralization reaction. As H + migrates, the soil/substrate mud between the two electrodes is gradually acidified, causing the contaminants to dissociate into the pore water. Under the action of an electric field, the dissociated pollutants migrate to the vicinity of the cathode along with pore water, one part of pollutants are removed through electroosmosis flow near the pumping cathode, and the other part of pollutants permeate to the inner side of the ion exchange membrane and undergo neutralization and precipitation reaction with OH ‑ accumulated at the cathode, so that autonomous and controllable electric acidification dissociation removal of soil/substrate pollutants is realized.
Description
Technical Field
The invention relates to the field of resource protection and environmental treatment, in particular to an electric acidification and dissociation device and method for autonomously controllable soil or substrate sludge pollutants.
Background
At present, the soil and river and lake sediment in many countries and regions of the world are severely polluted by heavy metals and the like. Pollution of soil and river and lake sediment brings a series of serious problems, and the grain safety and the human living environment are gradually threatened. The electric repairing technology is a technology capable of separating pollutants from soil/substrate sludge, and the principle is that the pollutants are separated and removed from the soil/substrate sludge by means of electromigration or electroosmosis under the action of an electric field. The electric repair technology is still in the development stage as an emerging technology, and the problem of unbalanced pH and focusing effect generated by electrode polarization in the electrolysis process are main technical bottlenecks for restricting the application and development of the technology.
The electrolytic water anode in the electrokinetic remediation process generates O 2 and H +, and the cathode generates H 2 and OH -, and the reaction equation is as follows:
anode 2H 2O-4e-→O2+4H+(E0 = -1.229V
Cathode 2H 2O+2e-→H2+2OH-(E0 = -0.828V
The H + generated by the anode makes the anode region acidic, and the OH - generated by the cathode makes the cathode region alkaline. Positively charged H + migrates toward the cathode and negatively charged OH - migrates toward the anode, forming an acidic migration zone and an alkaline migration zone, decreasing the anode pH to below 3 and increasing the cathode pH to above 12 in a short period of time. OH - generated in the cathode region and heavy metal ions form hydroxide precipitates, so that pollutants can only directionally migrate within a certain range, and complete separation of the pollutants (namely a focusing effect) cannot be realized. Meanwhile, pH change caused by bipolar solution migration can influence the adsorption-desorption, precipitation-dissolution and electroosmosis flow direction and speed of ions in soil, and directly or indirectly has great influence on the existence form and migration characteristics of pollutants in soil/sediment, thereby influencing the pollutant removal efficiency. The anode is corroded in a lower pH environment, and metal ions are deposited on the cathode surface, so that the current efficiency and the pollutant removal rate are greatly reduced. Thus, controlling the directional migration of H + during electrokinetic remediation, allowing sufficient H + to acidify dissociated contaminants is critical to improving electrokinetic remediation techniques.
In recent years, in order to solve the problem of autonomous acidification and dissociation of pollutants in the electric repair process, many scientific researchers have made many researches on the aspects of power-on mode, process combination optimization, electrode structure improvement, electrolyte regulation and the like. At present, a plurality of technical devices for electrically repairing soil/substrate sludge are disclosed at home and abroad. The patent with publication number CN103962372A discloses a device for repairing cesium-polluted soil by a cathode approximation method and a repairing method thereof, the treatment method of the device is to fix a cathode, change the use of an anode along with the progress of electric repairing, continuously approximate the pollutants to the cathode, concentrate cesium pollutants in the soil in a specific cathode area, thereby effectively migrating cesium pollutants out of the polluted soil, reducing the volume of the polluted soil, and then adsorbing and recycling the cesium pollutants by adopting an adsorption material. The patent with publication number CN106881339A discloses a device and a method for removing heavy metals in soil by combining assembled in-situ leaching and EKG electric co-operation, the device acidizes and elutes in situ under the action of a leaching agent such as FeCl 3 and the like, heavy metals are migrated by the action of an electric field, and the leached heavy metal solution is separated and stored from a soil layer, so that water-soil separation of the heavy metals is realized. Publication CN100429507C discloses a method of controlling and preventing cathode OH - diffusion by a glass sleeve with a bottom ceramic core, which achieves no increase in anode pH after power-on. Patent publication No. CN203875110U discloses an electric remediation device with controllable soil pH, which adjusts pH near an electrode plate by adding buffer solution to a cathode and an anode respectively. The patent with publication No. CN102527707A discloses an enhanced electrokinetic remediation method for heavy metal contaminated soil, which is characterized in that an active material layer is attached to the surface of a graphite or metal electrode at the anode and cathode to form an integrated composite electrode with permeable reaction performance, OH - generated by the reaction of a cathode permeable reaction layer and an adsorption electrode is utilized to avoid the pH rise of the cathode soil, and meanwhile, heavy metals adsorbed and migrated are captured. Patent publication No. CN206527153U discloses an electrodynamic remediation device for heavy metal contaminated soil, which avoids premature precipitation of metal ions through a cation selective permeable membrane on one side of a cathode, and accelerates metal removal.
The inventor has found that in the process of implementing the invention: the existing electric repair pH control device or technology has larger defects: (1) By adopting a cathode approximation method, the electrode position needs to be replaced frequently, and the problems of anode acidification and cathode alkalization in the electric repairing process are not solved in practice; (2) By adopting a buffer solution or a leaching agent method, chemical reagents are required to be added, the cost is high, and secondary pollution is possibly caused by adding the chemical reagents; (3) The composite electrode, the permeable reaction wall or the electrode structure improvement mode is adopted, the essence of the composite electrode is that OH - generated by the reaction of the adsorption electrode is neutralized, the composite electrode cannot be reused after repair is finished, and the cost is high; (4) The existing cation exchange membrane technology gathers a large amount of OH - on the cathode and can not timely separate the electromigration metal cations and other pollutants, which can cause a large amount of sediment to be accumulated on the surfaces of the membrane and the electrode, so that the membrane and the electrode are polluted.
In summary, H + and OH - are generated in the electric repairing process, measures are taken to realize the control of the pH of the polluted soil/sediment, H + generated spontaneously by an anode in the electric repairing process is utilized to prevent the OH - from migrating to the anode to contact with H +, so that the focusing effect in the electric repairing process is avoided, the polluted soil/sediment is acidified in the process of gradually migrating H +, the dissociation rate of pollutants in the polluted soil/sediment is improved, and the method is a new idea for solving the pollution problem, and has great environmental, economic, social benefits and application prospects.
Disclosure of Invention
The invention provides an autonomous controllable electric acidification dissociation device and method for soil or sediment pollutants, which can prevent OH - migration of a cathode, gradually migrate to the cathode by utilizing H + spontaneously generated by an anode in an electric restoration process under the condition of not adding leaching chemical reagents, acidify polluted soil/sediment, improve the dissociation degree of the soil/sediment pollutants, and have simple operation and small ecological environment interference on the soil/sediment.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The utility model provides an automatic controllable soil or substrate sediment pollutant electronic acidolysis device, includes direct current steady voltage power supply, the scrubbing electrode that links to each other with direct current steady voltage power supply, the scrubbing electrode divide into relative parallel arrangement's positive pole and negative pole, link to each other with direct current steady voltage power supply's positive pole and negative pole respectively, the positive pole includes that hole-free organic glass board, water guide electrode plate, locate the foraminiferous organic glass board on water guide electrode plate right side, locate the filter screen outside foraminiferous organic glass board, water guide electrode plate and hole-free organic glass board interval airtight form the fluid replacement groove cavity, the moisturizing pipe with fluid replacement groove cavity intercommunication is used for to the fluid replacement groove cavity moisturizing is in order to realize the stable production of positive pole H + and to the negative pole migration; the cathode comprises a filter screen, a perforated organic glass plate, an ion exchange membrane, a water guide electrode plate, a non-porous organic glass plate and a pore water storage tank which are sequentially arranged, wherein the pore water storage tank is communicated with a cavity formed between the perforated organic glass plate and the ion exchange membrane, and the ion exchange membrane is used for isolating OH - generated by electrolyzed water so that more H + migrates to the vicinity of the cathode.
Furthermore, the anode also comprises an electrode mounting cover plate, the pore-free organic glass plate, the water guide electrode plate, the porous organic glass plate and the filter screen of the anode part are sequentially fixed at proper intervals through clamping grooves on the electrode mounting cover plate, and the bottom is sealed and fixed on a triangular cone-shaped base.
Further, the cathode also comprises an electrode mounting cover plate, a filter screen of the cathode part, a porous organic glass plate, an ion exchange membrane, a water guide electrode plate and a pore-free organic glass plate are fixed at proper intervals in sequence through clamping grooves on the electrode mounting cover plate, and the bottom of the cathode is in sealing connection with the pore water storage groove.
Furthermore, the pore water storage tank adopts a structure with an upper square column shape and a lower inverted triangle cone shape.
Further, the perforated plexiglass plate is the same as the openings of the screen in height and width.
Further, the pore water storage tank is connected with a pore water discharge conduit, the pore water discharge conduit is connected with a peristaltic pump, and the peristaltic pump can be communicated with a water supplementing pipe to supplement water to a liquid supplementing tank cavity formed between the water guiding electrode plate and the pore-free organic glass plate through the water supplementing pipe after acidification of the area near the anode reaches a certain pH range.
Further, the anode and cathode of the scrubbing electrode are generally wedge-like in configuration after assembly, having a height of about 25cm and a thickness of about 4cm.
Furthermore, one side of the non-porous organic glass plate is marked with scale marks from bottom to top.
Further, the two sides of the water guide electrode plate are provided with water guide grooves which are uniformly and vertically arranged, a metal wire connected with a waterproof wire is arranged inside the water guide electrode plate, and the waterproof wire is connected to a direct-current stabilized power supply.
An electric acidolysis method for autonomously controllable soil or substrate sludge pollutants, which is carried out by adopting the device, comprises the following steps:
after the area to be treated is selected, the soil removing electrode is inserted into soil/sediment, and the distance between two adjacent soil removing electrodes is not more than 2.0m;
D.C. regulated power supply is applied, pore water in the soil/sediment to be treated is subjected to electrolytic reaction, H + is generated at the anode, OH - is generated at the cathode, H + is subject to cathode migration under the action of an electric field, an ion exchange membrane prevents OH - from migrating to the anode and from contacting with H +, along with migration of H +, the acidity of surface soil/sediment is increased, dissolution, desorption and mass release of soil/sediment pollutants are promoted, and the soil/sediment pollutants are separated and enter into water in a pore space;
Under the action of a direct current electric field, metal ions and NH 4 +、H+ cations in soil/sediment are directionally migrated to a cathode water guide electrode plate, PO 4 3-,Cl-、SO4 2-、OH- anions are directionally migrated to an anode water guide electrode plate, and pollutants entering pore water are directionally migrated from the anode water guide electrode plate to the cathode water guide electrode plate along with the pore water under the electroosmosis effect while the electromigration occurs, so that the dual effects of the electromigration and the electroosmosis are received, and the pollutants and the pore water are effectively separated from the soil/sediment to be treated;
Under the action of a direct current electric field, pollutants or pore water migrating to the vicinity of the cathode of the decontamination electrode sequentially pass through a filter screen and a perforated organic glass plate, enter a cavity formed between the perforated organic glass plate and an ion exchange membrane, then enter a pore water storage tank, a pore water discharge conduit is connected with a peristaltic pump, and the pore water stored in the pore water storage tank and the pollutants contained in the pore water are automatically separated and discharged from soil/sediment media in a centralized manner; the other part of pollutants permeated into the inner side of the ion exchange membrane are subjected to neutralization and precipitation reaction with high-concentration OH - generated between the ion exchange membrane and the cathode water guide electrode plate to be removed;
In the running process, the pH value of the area near the anode and the pore water yield of the peristaltic pump near the cathode are monitored, when the anode acidizing reaches a certain pH range (for example, less than 3.0), the peristaltic pump is connected with the water supplementing pipe, water is supplemented to the anode, and when the pore water yield of the peristaltic pump is obviously reduced, the electric dehydration and decontamination operation can be stopped.
By adopting the scheme, the invention can control the pH value in the electric repair process and has the following beneficial effects:
(1) H + generated spontaneously by the anode in the electric repairing process is used for providing a source of H + for soil/sediment acidification and dissociation, and the stable generation of the anode H + and migration to the cathode can be realized under the action of an electric field by supplying water near the anode. Under the action of an electric field, H + and dissociated cationic pollutants thereof are transported and discharged to one side of the cathode along with water, so that acidification of the restored soil/substrate sludge is realized, the activated dissociation of the pollutants can be realized without adding chemical reagents, and the electric restoration efficiency is effectively improved;
(2) Through the ion exchange membrane, OH - generated by cathode electrolysis is prevented from migrating to the anode, contact and reaction with H + are avoided, H + can migrate to the cathode completely, acidification of soil/substrate sludge between the electrodes is realized, cationic pollutants and the like can penetrate through the ion exchange membrane, and the cationic pollutants and the OH - meet with the inner side of the membrane to be directly precipitated; the ion exchange membrane also avoids the deposition of OH - and the transferred cations near the cathode area, and realizes the fundamental conversion from electrokinetic migration enrichment of pollutants to effective separation of the pollutants from soil/sediment in the in-situ electrokinetic remediation process.
Drawings
FIG. 1 is a schematic diagram of the working principle of an autonomous controllable electric acidification dissociation device for soil or sediment pollutants;
FIG. 2 is a schematic view of the structure of an anode in the scrubbing electrode of the present invention;
FIG. 3 is a schematic view of the structure of a cathode in the scrubbing electrode of the present invention;
Fig. 4 is a schematic structural view of a water-guiding electrode plate according to the present invention.
In the figure: 1-direct current stabilized power supply, 2-polluted soil/sediment, 3-peristaltic pump, 4-1-waterproof wire, 4-2-water guide electrode plate, 4-3-filter screen, 4-4-perforated organic glass plate, 4-5-nonporous organic glass plate, 4-6-electrode mounting cover plate, 4-7-ion exchange membrane, 4-8-pore water storage tank, 4-9-pore water discharge conduit, 4-10-water supplementing pipe and 5-rubber hose.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings.
Referring to fig. 1-3, one embodiment of the river and lake polluted bottom mud in-situ decrement decontamination device based on pore water guide and discharge of the invention comprises a direct current stabilized power supply 1, and a decontamination electrode connected with the direct current stabilized power supply 1, wherein the decontamination electrode is divided into a cathode (shown in fig. 2) and an anode (shown in fig. 3), wherein the cathode part is connected with the cathode of the direct current stabilized power supply 1 and comprises a waterproof wire 4-1, a water guide electrode plate 4-2, a filter screen 4-3, a porous organic glass plate 4-4, a non-porous organic glass plate 4-5, an electrode mounting cover plate 4-6, an ion exchange membrane 4-7, a pore water storage tank 4-8 and a pore water discharge conduit 4-9; the anode part is connected with the anode of the direct current stabilized power supply 1 and comprises a waterproof lead 4-1, a water conducting electrode plate 4-2, a filter screen 4-3, a perforated organic glass plate 4-4, a non-porous organic glass plate 4-5, an electrode mounting cover plate 4-6 and a water supplementing pipe 4-10.
The water-conducting electrode plate 4-2 is a universal electrode and is made of graphite material, and can be used as an anode or a cathode. In this embodiment, there are 2 water-guiding electrode plates, which are respectively located at the anode and the cathode, are relatively parallel to each other, and are respectively connected to the anode and the cathode of the dc stabilized power supply 1, where the dc stabilized power supply 1 has a digital display function, and the voltage and current are adjustable, and the circuit control (power supply on-off, power-on time control, current/voltage adjustment) and the electricity consumption metering device of the whole river and lake polluted substrate sludge in-situ decrement and decontamination device based on pore water drainage are both considered.
Referring to fig. 4, a water-guiding electrode plate 4-2 is installed below an electrode installation cover plate 4-6, a vertical water-guiding groove 4-2-1 and a metal wire 4-2-2 are arranged on the water-guiding electrode plate 4-2, the metal wire 4-2-2 penetrates through the electrode installation cover plate 4-6 to be connected with a waterproof wire 4-1 after penetrating out of the electrode plate, and the waterproof wire 4-1 is connected with a direct-current regulated power supply 1.
As shown in FIG. 2, the water guide electrode plate 4-2 on the anode side and the non-porous organic glass plate 4-5 are sealed at intervals to form a fluid supplementing groove cavity with a distance of 15mm, and the water supplementing pipe 4-10 penetrates through the electrode mounting cover plate 4-6 to be connected with the fluid supplementing groove cavity. The outside of the water guide electrode plate 4-2 is provided with a perforated organic glass plate 4-4 at a certain distance, a filter screen 4-3 is laid on the outside of the perforated organic glass plate 4-4, and the perforated organic glass plate 4-4 is fixedly arranged below the electrode mounting cover plate 4-6. The electrode plate component at one side of the anode is sequentially provided with a pore-free organic glass plate 4-5, a water conducting electrode plate 4-2, a porous organic glass plate 4-4 and a filter screen 4-3, and is fixed at proper intervals in sequence through clamping grooves on an electrode mounting cover plate 4-6, and the bottom is sealed and fixed on a triangular cone-shaped base; the electrode plate component on the cathode side is sequentially provided with a filter screen 4-3, a perforated organic glass plate 4-4, an ion exchange membrane 4-7, a water conducting electrode plate 4-2 and a non-porous organic glass plate 4-5.
As shown in FIG. 3, the pore-free organic glass plate 4-5, the water conducting electrode plate 4-2, the ion exchange membrane 4-7, the porous organic glass plate 4-4 and the filter screen 4-3 are sequentially assembled, the bottom of the water conducting electrode plate 4-2 is provided with a pore water storage tank 4-8, and the pore water storage tank 4-8 is communicated with a cavity formed between the porous organic glass plate 4-4 and the ion exchange membrane 4-7, and is kept sealed with the water conducting electrode plate 4-2. The perforated organic glass plate 4-4 is fixedly arranged below the electrode mounting cover plate 4-6, and a filter screen 4-3 is laid outside the perforated organic glass plate 4-4.
The pore water storage tank 4-8 is connected with the pore water discharging conduit 4-9, the pore water discharging conduit 4-9 is connected with the peristaltic pump 3 through a rubber tube, and the peristaltic pump 3 pumps and discharges the pore water stored in the pore water storage tank 4-8 and the pollutants contained in the pore water. The pore water storage tanks 4-8 can adopt an inverted triangular pyramid structure, so that pore water can be conveniently stored and plugged in soil/sediment.
The perforated organic glass plate 4-4 has a structure that the middle and lower parts are provided with holes and the upper parts are not provided with holes, and the heights and the widths of the holes of the perforated organic glass plate 4-4 and the filter screen 4-3 are completely the same. The double filtration interception of the perforated organic glass plate 4-4 and the filter screen 4-3 prevents the surface layer sediment particles from invading along with the loss of pore water and blocking the water guide groove 4-2-2 of the water guide electrode plate 4-2 in the electric dehydration and decontamination process. Graduation marks are marked on one side of the nonporous organic glass plate 4-5 from bottom to top and are used for determining the depth of the electrode plate inserted into the polluted soil/sediment. The anode and the cathode of the decontamination electrode are in a wedge-shaped structure after being assembled, the height of the decontamination electrode is about 25cm, the thickness of the decontamination electrode is about 4cm, and the length of the decontamination electrode can be flexibly adjusted according to the actual situation of a field.
The application method and principle of the river and lake polluted bottom mud in-situ decrement and decontamination device based on pore water drainage are as follows:
The decontamination electrode is inserted into the bottom mud 2, after the direct current stabilized power supply 1 is connected, under the action of a direct current electric field, metal ions (cations such as M n+)、NH4 +、H+ and the like are directionally migrated to the water guide electrode plate 4-2 on the cathode side, and anions such as PO 4 3-、Cl-、SO4 2-、OH- and the like are directionally electromigration to the water guide electrode plate 4-2 on the anode side), and pollutants entering pore water can be directionally migrated from the anode water guide electrode plate 4-2 to the cathode water guide electrode plate 4-2 along with the pore water at the same time of electromigration.
After the power is applied, an electrolytic water reaction occurs in the vicinity of the water-conducting electrode plate 4-2 connected to the water-proof wire 4-1, and H + and OH - are formed. After the pH value of the area near the anode reaches a certain pH value range through monitoring, namely, water is supplemented into a liquid supplementing groove cavity formed between the water guiding electrode plate 4-2 and the nonporous organic glass plate 4-5 through the water supplementing pipe 4-10, H + generated by the anode migrates to the cathode under the effects of an electric field, electroosmosis and a hydraulic gradient, so that the polarization phenomenon at one side of the anode is relieved. On the side of the cathode water-conducting electrode plate 4-2, due to the existence of the ion exchange membrane 4-7, OH - generated by electrolysis of water is isolated, so that focusing effect between the cathode and the anode is inhibited, namely more H + can migrate to the vicinity of the cathode, and the increase of H + can promote the dissolution and release of pollutants in the bottom mud and increase the concentration of the pollutants in the pore water. Therefore, under the dual functions of electroosmosis and electromigration, the separation of pollutants and pore water from the surface layer sediment medium is realized. The polarization phenomenon on one side of the anode is weakened through water supplementing, H + generated by polarization is fully utilized, and the focusing effect is effectively restrained by the ion exchange membrane 4-7, so that the efficiency of pore water drainage is improved.
Soil/substrate sludge pollutants or pore water molecules migrating to the vicinity of the cathode of the decontamination electrode sequentially pass through the filter screen 4-3 and the perforated organic glass plate 4-4, enter a cavity formed between the perforated organic glass plate 4-4 and the ion exchange membrane 4-7, and then are collected into the pore water storage tank 4-8 under the action of gravity. Under the action of the ion exchange membrane 4-7, OH - generated at the cathode is accumulated in the cavity between the water conducting electrode plate 4-2 and the ion exchange membrane 4-7. Part of pollutants can enter the cavity between the water guide electrode plate 4-2 and the ion exchange membrane 4-7 through the ion exchange membrane 4-7 to be subjected to neutralization and precipitation reaction with OH-, so that the precipitation separation of the pollutants is realized. Under the condition that the water guide electrode plate 4-2 is not electrified, the pore water storage tank 4-8 can also collect and discharge pore water in bottom mud above the water guide electrode plate 4-2 in a concentrated manner.
Ion exchange membranes are selectively permeable to ions of different charge. The cation membrane only allows cations to pass through and prevents anions from passing through. Under the action of an external direct current electric field, ions in water directionally migrate. The preparation method is that linear high polymer material polyethylene is used as a carrier to prepare a film, styrene is used as a functional group monomer for introducing an ion exchange group, and divinylbenzene is used as a crosslinking agent; the polyethylene film is prepared through impregnating styrene and divinylbenzene, water phase heating and copolymerizing grafting in the presence of initiator, and final sulfonating with concentrated sulfuric acid. The ion exchange membrane has low resistivity, 3.5 omega cm 2 of membrane surface resistance, excellent conductivity, low energy consumption, high selective permeability, thickness of less than 0.3mm, exchange capacity of about 2meq/g, selective permeability of more than 98 percent and current density of less than 100mA/cm 2.
According to the invention, the ion exchange membrane 4-7 is arranged on the cathode to isolate OH - generated by the cathode, H + generated by the anode migrates to the cathode under the action of an electric field, and along with migration of H +, soil/sediment between the two electrodes is gradually acidified, so that pollutants in the soil/sediment are dissociated into pore water. Under the action of an electric field, the dissociated pollutants migrate to the vicinity of the cathode along with pore water, one part of the pollutants are removed through electroosmosis flow near the pumping cathode, and the other part of the pollutants permeate to the inner side of the ion exchange membrane 4-7 and are subjected to precipitation and neutralization reaction with OH - accumulated on the cathode, so that the polluted soil/sediment is repaired.
The invention uses a pair of decontamination electrodes and an ion exchange membrane to divide the polluted soil/substrate sludge into an acid-producing region, a pollutant acidolysis region, a pollutant separation and removal region and an alkali-producing region. The anode of the decontamination electrode is an acid-producing region, the region between the cathode and the anode of the decontamination electrode is a pollutant acidification dissociation region, the region between the filter screen 4-3 of the cathode of the decontamination electrode and the ion exchange membrane 4-7 is a pollutant separation region, and the region between the ion exchange membrane 4-7 and the water guide electrode plate 4-2 of the cathode of the decontamination electrode is an alkali-producing region.
In the acid-producing area, the electrolysis acid-producing reaction is mainly carried out on the anode under the electrified condition, H + is driven to migrate to the pollutant acidification dissociation area by supplementing water, and the pH value near the anode is kept not lower than a certain set value. The main reactions that occur in this region are: 2H 2O-4e-→O2+4H+.
In the pollutant acidification dissociation region, mainly, the pollutants undergo acidification dissociation and ion exchange under the action of H +, and at the same time, positively charged pollutant ions migrate to the vicinity of the cathode under the action of an electric field. The main reactions taking place in this region are ：H++MxOy→Mn++H2O,H++M(OH)n→Mn++H2O,H++R-Mn+→Mn++R-H+.
In the pollutant separation zone, the pollutants are directionally moved under the action of an electric field and enter the pore water storage tank 4-8 along with electroosmosis flow to realize the separation of the pollutants from soil/bottom mud, and the pollutants in the pore water storage tank 4-8 can be discharged by a peristaltic pump.
In the alkali producing area, the cathode plate is subjected to electrolytic alkali producing reaction under the electrified condition, and OH - cannot migrate due to the isolation effect of the ion exchange membrane until a large amount of pollutants on one side of the anode migrate to the rear, so that the neutralizer precipitation reaction occurs.
The following describes the implementation process with reference to fig. 1,2 and 3:
1. the environment of the field to be treated and the pollution condition of the soil/substrate sludge 2 are known, and the pollution condition comprises basic parameters such as the content and distribution of pore water in the upper soil/substrate sludge 2, the type, the content and the distribution of pollutants and the like. The depth of insertion of the scrubbing electrode into the soil/substrate 2, etc. is determined based on other environmental conditions of the site to be treated and the occurrence characteristics of the main contaminants in the soil/substrate 2. In general, the soil/sediment 2 with the surface layer of 0-10cm has high pore water content and the water content is 70% -90%; as the depth of the soil/sediment 2 increases, the pore water content generally tends to decrease, and when the thickness of the soil/sediment 2 exceeds 30cm, the water content is generally lower than 50%. In order to improve the dewatering and decontamination efficiency of the soil/substrate sludge 2, it is generally recommended to select a surface layer 20cm of soil/substrate sludge 2 with high concentration of contaminants and active release of pore water for treatment.
2. After the area to be treated is selected, the soil removal electrode is inserted into the soil/sediment 2, and whether the soil removal electrode is inserted into the set depth is generally confirmed according to the scale marks on one side of the non-porous organic glass plate 4-5 of the soil removal electrode. In order to reduce the influence of the direct current electric field on the soil/sediment ecological environment, the energizing voltage of the decontamination electrodes is generally not more than 30V, the distance between two adjacent decontamination electrodes is not more than 2.0m, and the voltage gradient is controlled within 1V/cm.
3. And (3) switching on a direct-current stabilized power supply 1, and generating electrolytic reaction on pore water in the soil/sediment 2 to be treated, wherein H + is generated at an anode and OH - is generated at a cathode. Under the action of an electric field, H+ can migrate to the cathode, while the ion exchange membrane 4-7 prevents OH - from migrating to the anode, and avoids contact with H +. On the cathode water-conducting electrode plate 4-2 side, focusing effect is suppressed due to the presence of the ion exchange membrane 4-7. With the migration of H +, the acidity of the surface soil/sediment is increased, the dissolution, desorption and mass release of soil/sediment pollutants are promoted, the soil/sediment pollutants are separated, and the soil/sediment pollutants enter into the pore water.
4. Under the action of a direct current electric field, cations such as metal ions and NH 4 +、H+ in soil/sediment 2 directionally migrate to the cathode water guide electrode plate 4-2, and anions such as PO 4 3-,Cl-、SO4 2-、OH- directionally migrate to the anode water guide electrode plate 4-2. While electromigration occurs, contaminants entering the pore water also directionally migrate with the pore water from the anode water electrode plate 4-2 to the cathode water electrode plate 4-2 under the electroosmosis effect. The pollutants and pore water are effectively separated from the soil/sediment 2 to be treated under the double effects of electromigration and electroosmosis.
5. The two sides of the water guide electrode plate 4-2 are provided with uniform water guide grooves 4-2-2, and the vertical arrangement is prioritized. The water-conducting electrode plate 4-2 belongs to a general electrode and can be used as an anode or a cathode, an internal metal wire 4-2-1 of the water-conducting electrode plate 4-2 is connected with a waterproof wire 4-1 and is used for supplying power to the water-conducting electrode plate 4-2, and the water-conducting electrode plate 4-2 can be processed by conductive materials such as graphite and the like.
6. Under the action of the direct current electric field, pollutants or pore water which migrates to the vicinity of the cathode of the decontamination electrode sequentially pass through the filter screen 4-3 and the perforated organic glass plate 4-4 and enter a cavity formed between the perforated organic glass plate 4-4 and the ion exchange membrane 4-7. The filter screen 4-3 is made of fiber or cotton-flax material, and the aperture and the thickness are not more than 1mm; the aperture of the perforated organic glass plate 4-4 is not more than 5mm, and the thickness is not more than 3mm. The height of the openings of the filter screen 4-3 and the perforated organic glass plate 4-4 is the same as the depth of the soil/substrate sludge 2 to be treated, and is generally 20cm.
7. Outside the perforated plexiglass plate 4-4 is a screen 4-3. Through double filtration interception of the perforated organic glass plate 4-4 and the filter screen 4-3, surface soil/sediment particles are effectively prevented from invading along with the loss of pore water in the electric dehydration and decontamination process and the water guide groove 4-2-2 of the water guide electrode plate 4-2 is blocked.
8. Under the action of electric field or gravity, the soil/sediment pore water migrating to the vicinity of the cathode water guide electrode plate 4-2 continues to flow into the pore water storage tank 4-8 along the cavity formed between the perforated organic glass plate 4-4 and the ion exchange membrane 4-7. The pore water storing tank 4-8 adopts an upper square column and a lower inverted triangle cone structure, which is convenient for plugging in the soil/sediment 2.
9. The upper square part of the pore water storage tank 4-8 is transversely connected with a pore water discharging conduit 4-9. The pore water discharging conduit 4-9 is connected with the peristaltic pump 3 through the rubber hose 5, and the pore water stored in the pore water storage tank 4-8 and the pollutants contained in the pore water are automatically separated and discharged from the soil/sediment 2 medium in a centralized way; the other part of the pollutants permeated into the inner side of the ion exchange membrane 4-7 is removed by neutralization and precipitation reaction with high-concentration OH - generated between the ion exchange membrane 4-7 and the cathode water guide electrode plate 4-2.
10. The soil/sediment in-situ decontamination electrode is powered by a direct current stabilized power supply 1 and a waterproof wire 4-1. The direct current stabilized power supply 1 has a digital display function, and can measure the power consumption and control the power-on time, wherein the voltage and the current are adjustable. To save energy consumption, the scrubbing electrode is generally operated in an intermittent power-on mode. During the power outage, the water guide groove 4-2-2 of the water guide electrode plate 4-2 can collect pore water in the soil/sediment 2 above the water guide electrode plate 4-2 by means of gravity.
11. During operation, the pH of the area near the anode and the pore water output of peristaltic pump 3 near the cathode were monitored. When the anode acidizing reaches a certain pH range, the peristaltic pump 3 is connected with the water supplementing pipe 4-10, and water is added to the anode. When the pore water outlet of the peristaltic pump 3 is obviously reduced, the electric dehydration and decontamination operation can be stopped, the decontamination electrode is pulled out, and the operation is continued after proper flushing.
12. The decontamination electrode-2 of the device has the characteristics of generalization and standardization and can be used as an anode or a cathode. In specific practice, a plurality of decontamination electrodes can be combined or concentrated, so that the treatment area of a single decontamination electrode is greatly increased, and the operation efficiency of the device is improved by means of concentrated power supply and unified drainage of pore water.
The invention carries out in-situ transverse migration and longitudinal collection on the surface layer substrate sludge pollutants along with pore water under the action of a low-voltage safe direct current electric field and a gravity field. An ion exchange membrane is additionally arranged on one side of the cathode of the electric repairing device to prevent OH - generated by cathode electrolysis from migrating. Under the action of an electric field, H + generated by anodic electrolysis migrates to a cathode, OH - generated by the cathode is isolated by an ion exchange membrane and is accumulated on the inner side of the ion exchange membrane, so that the H + cannot migrate to the anode under the action of the electric field, and the H + is prevented from contacting and carrying out neutralization reaction. As H + migrates, the soil/substrate mud between the two electrodes is gradually acidified, causing the contaminants to dissociate into the pore water. Under the action of an electric field, the dissociated pollutants migrate to the vicinity of the cathode along with pore water, one part of pollutants are removed through electroosmosis flow near the pumping cathode, and the other part of pollutants permeate to the inner side of the ion exchange membrane and undergo neutralization and precipitation reaction with OH - accumulated at the cathode, so that autonomous and controllable electric acidification dissociation removal of soil/substrate pollutants is realized.
Claims (8)
1. The utility model provides an electronic acidolysis dissociation device of independently controllable soil or substrate mud pollutant, includes direct current stabilized power supply (1), the scrubbing electrode that links to each other with direct current stabilized power supply (1), the scrubbing electrode divide into relative parallel arrangement's positive pole and negative pole, links to each other its characterized in that with the positive pole and the negative pole of direct current stabilized power supply (1) respectively: the anode comprises a non-porous organic glass plate (4-5), a water guide electrode plate (4-2), a porous organic glass plate (4-4) arranged on the right side of the water guide electrode plate (4-2), a filter screen (4-3) arranged on the outer side of the porous organic glass plate (4-4), wherein the water guide electrode plate (4-2) and the non-porous organic glass plate (4-5) are sealed at intervals to form a liquid supplementing groove cavity, and a water supplementing pipe is communicated with the liquid supplementing groove cavity and is used for supplementing water to the liquid supplementing groove cavity so as to realize stable generation of anode H + and migration to a cathode; the cathode comprises a filter screen (4-3), a perforated organic glass plate (4-4), an ion exchange membrane (4-7), a water guide electrode plate (4-2) and a non-porous organic glass plate (4-5) which are sequentially arranged, and a pore water storage tank (4-8) arranged at the bottom of the water guide electrode plate (4-2), wherein the pore water storage tank (4-8) is communicated with a cavity formed between the perforated organic glass plate (4-4) and the ion exchange membrane (4-7), and the ion exchange membrane (4-7) is used for isolating OH - generated by electrolytic water so as to enable more H + to migrate to the vicinity of the cathode; the anode also comprises an electrode mounting cover plate (4-6), wherein the pore-free organic glass plate (4-5), the water guide electrode plate (4-2), the porous organic glass plate (4-4) and the filter screen (4-3) of the anode part are fixed at proper intervals in sequence through clamping grooves on the electrode mounting cover plate (4-6), and the bottom is sealed and fixed on a triangular cone-shaped base; the cathode also comprises an electrode mounting cover plate (4-6), a filter screen (4-3) of the cathode part, a perforated organic glass plate (4-4), an ion exchange membrane (4-7), a water guide electrode plate (4-2) and a non-perforated organic glass plate (4-5) are fixed at proper intervals in sequence through clamping grooves on the electrode mounting cover plate, and the bottom is in sealing connection with a pore water storage tank (4-8).
2. The autonomous controlled electric acidification dissociation device of soil or substrate contaminants of claim 1, wherein: the pore water storage tank (4-8) adopts a structure with square column at the upper part and inverted triangle cone at the lower part.
3. The autonomous controlled electric acidification dissociation device of soil or substrate contaminants of claim 1, wherein: the height and width of the openings of the perforated organic glass plate (4-4) and the filter screen (4-3) are the same.
4. The autonomous controlled electric acidification dissociation device of soil or substrate contaminants of claim 1, wherein: the pore water storage tank (4-8) is connected with the pore water discharging conduit (4-9), the pore water discharging conduit (4-9) is connected with the peristaltic pump (3), the peristaltic pump (3) can be communicated with the water supplementing pipe to supplement water to a liquid supplementing tank cavity formed between the water guiding electrode plate (4-2) and the nonporous organic glass plate (4-5) after acidification of the area near the anode reaches a certain pH range.
5. The autonomous controlled electric acidification dissociation device of soil or substrate contaminants of claim 1, wherein: the anode and cathode of the scrubbing electrode are generally wedge-shaped in configuration with a height of about 25cm and a thickness of about 4cm after assembly.
6. The autonomous controlled electric acidification dissociation device of soil or substrate contaminants of claim 1, wherein: graduation lines are marked on one side of the non-porous organic glass plate (4-5) from bottom to top.
7. The autonomous controlled electric acidification dissociation device of soil or substrate contaminants of claim 1, wherein: the double sides of the water guide electrode plate (4-2) are provided with water guide grooves (4-2-2) which are uniformly and vertically arranged, a metal wire (4-2-1) connected with a waterproof wire (4-1) is arranged inside the water guide electrode plate (4-2), and the waterproof wire (4-1) is connected with a direct current stabilized power supply (1).
8. An autonomous controllable electric acidification dissociation method for soil or substrate sludge pollutants is characterized by comprising the following steps of: which is carried out with the device according to any one of claims 1-7, which method comprises the steps of:
After the area to be treated is selected, the soil/sediment (2) is inserted into the soil/sediment, and the distance between two adjacent soil removing electrodes is not more than 2.0m;
the direct current stabilized power supply (1) is connected, pore water in the soil/sediment (2) to be treated is subjected to electrolytic reaction, H + is respectively generated at the anode, OH - is generated at the cathode, H+ is migrated to the perineum under the action of an electric field, the ion exchange membrane (4-7) prevents OH - from migrating to the anode, contact with H + is avoided, the acidity of surface soil/sediment is increased along with migration of H +, dissolution, desorption and mass release of soil/sediment pollutants are promoted, and the soil/sediment pollutants are separated and enter into water in the pore;
Under the action of a direct current electric field, metal ions and NH 4 +、H+ cations in soil/sediment (2) directionally migrate to a cathode water guide electrode plate (4-2), PO 4 3-,Cl-、SO4 2-、OH- anions directionally migrate to the anode water guide electrode plate (4-2), and pollutants entering pore water directionally migrate to the cathode water guide electrode plate (4-2) along with the pore water under the electroosmosis effect, and are effectively separated from the soil/sediment (2) to be treated under the double actions of electromigration and electroosmosis;
Under the action of a direct current electric field, pollutants or pore water migrating to the vicinity of a cathode of a decontamination electrode sequentially pass through a filter screen (4-3) and a perforated organic glass plate (4-4), enter a cavity formed between the perforated organic glass plate (4-4) and an ion exchange membrane (4-7), then are converged into a pore water storage tank (4-8), a pore water discharge conduit (4-9) is connected with a peristaltic pump (3), and pore water stored in the pore water storage tank (4-8) and pollutants contained in the pore water are automatically separated and discharged from a soil/bottom mud (2) medium; the other part of pollutants permeated into the inner side of the ion exchange membrane (4-7) are subjected to neutralization and precipitation reaction with high-concentration OH - generated between the ion exchange membrane (4-7) and the cathode water guide electrode plate (4-2) to be removed;
in the running process, the pH value of the area near the anode and the pore water yield of the peristaltic pump (3) near the cathode are monitored, when the anode acidizing reaches a certain pH range, the peristaltic pump (3) is connected with the water supplementing pipe (4-10), water is supplemented to the anode, and when the pore water yield of the peristaltic pump (3) is obviously reduced, the electric dehydration and decontamination operation can be stopped.
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| CN107377612A (en) * | 2017-08-30 | 2017-11-24 | 清华大学 | A kind of method that electronic resistance heating in original position cooperates with repairing polluted soil and underground water |
| CN107746163A (en) * | 2017-11-22 | 2018-03-02 | 长江水利委员会长江科学院 | A kind of dystrophication sediment in-situ decrement decontamination apparatus based on pore water guide |
| CN207671889U (en) * | 2017-11-22 | 2018-07-31 | 长江水利委员会长江科学院 | A kind of dystrophication sediment in-situ decrement decontamination apparatus based on pore water guide |
| CN108213070A (en) * | 2018-01-10 | 2018-06-29 | 清华大学 | A kind of original position is electronic-device and method of electrochemistry collaboration repairing polluted soil and underground water |
| CN209866960U (en) * | 2019-03-01 | 2019-12-31 | 长江水利委员会长江科学院 | Autonomous controllable soil or sediment pollutant electric acidification dissociation device |
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