CN104843836A - Groundwater remediation method for in-situ electrolysis - Google Patents
Groundwater remediation method for in-situ electrolysis Download PDFInfo
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- CN104843836A CN104843836A CN201510226060.XA CN201510226060A CN104843836A CN 104843836 A CN104843836 A CN 104843836A CN 201510226060 A CN201510226060 A CN 201510226060A CN 104843836 A CN104843836 A CN 104843836A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a groundwater remediation method for in-situ electrolysis. An electrolytic device for use in an in-situ electrolytic well can be directly extended into a remediation well; depth of the electrolytic device in the remediation well can be adjusted according to the depth of groundwater pollutant distribution; according to LNAPL (light non-aqueous phase liquid), the device is properly close to the groundwater level; according to DNAPL (dense non-aqueous phase liquid), the device can arrive at the bottom of an unconfined aquifer. According to the characteristics of a catalytic electrode of the electrolytic device, the electrolytic device can generate OH free groups and other strong oxidants in the remediation well by electrolysis and directly oxidize the groundwater pollutants, thus achieving groundwater remediation; meanwhile, hydrogen atoms are generated in electrolysis and can participate in pollutant reduction reaction; the hydrogen atoms not used combine to generate hydrogen or hydrogen ions in water; power for electrolysis is from mains supply or other green powers (such as solar power); a power supply control system performs AC/DC power conversion, power storage and fixed voltage/current supply and outputs DC power to enable the electrolytic device in the remediation well to run throughout the day.
Description
Technical field
The invention relates to a kind for the treatment of process of underground water, and relate to a kind of electrolysis process now processing Polluted Groundwater especially
Background technology
For a long time, chloro-carbon solvent is modal organic pollutant in underground water, aliphatic hydrocarbon as chloride in trieline and zellon etc. (Chlorinated Aliphatic Hydrocarbons, CAHs).Two during the last ten years, the U.S. about have 80% super fund site (Superfund sites) and more than 3,000 Department of Defense is subordinate in unit (Department of Defense, DOD) site, all can find the trace of these two kinds of pollutents.And in Taiwan, chlorinated solvents as the Taoyuan County Radio Corporation of America (RCA) underground water (comprises vinylchlorid, 1,1-Ethylene Dichloride, 1,1-ethylene dichloride, cis-1, the pollutions such as 2-Ethylene Dichloride, 1，1，1-trichloroethane, trieline, zellon) pollued field, the underground water well at red down grandfather Ford mausoleum, Yi Ren village of Gaoxiong County great Liao township pollutes containing trieline and Gao Xiongtai moulds wooden land factory vinylchlorid pollution etc., all can find the existence of CAHs.Remove the time expended needed for chloro-carbon solvent pollutent in these underground water be difficult to estimate, and the environment level of these pollued fields to be promoted to the amount of money expended needed for national regulatory standard also will be very huge, estimate with the pollued field of the U.S., total charge is often up to billions of U.S. dollar.
CAHs because of its low water solubility and high boiling characteristic, and is classified as one of pollutent of the most difficult removal; Especially, when it is present in underground environment with DNAPLs (Dense Nonaqueous-Phase Liquid, the DNAPL) source of pollution heavier than water, the degree of difficulty in its process is often higher.In the past between 10 to 15 years, pump-and-treat system method (Pump & Treat processes) proved can not rapidly, economical and effectively process DNAPL pollution problem.And some emerging in recent years source of pollution remedial technologies (SourceRemediationTechnologies), as interfacial agent or ethanol rush row's method (Surfactant or Alcohol Flooding) and existing heat treating process (In Situ Thermal Treatment) etc., for some DNAPL pollued fields, prove effectively remove a large amount of source of pollution, also can reduce the pollution burst size of source of pollution.Applied Electrochemistry technical finesse groundwater pollutant is the regulation engineering method of a novelty, can to hardly degraded organic substance in water, in air, in soil mainly through oxidation mechanism, and the mode via direct oxidation or indirect oxidation removes, as utilized O
2be H in cathodic reduction
2o
2, generate OH radical subsequently, pollutant oxidation decomposed.Sometimes for accelerating the generation of OH radical, often a small amount of Fe is added in a liquid
2+, make it produce the reaction of similar Fenton, this technology is also called electrochemical peroxide and decomposes (electrochemical peroxidation).
Fossil energy is about to face the awkward situation of exhausting shortage on the other hand; the whole world also meets with the crisis that the impact of climatic variation not seen before and greenhouse warm up; carbon reduction has become recent trend trend; countries in the world there's no one who doesn't or isn't replace traditional energy for important item to develop green energy resource science and technology; Taiwan is positioned at the subtropical zone of sunshine amount abundance; be applicable to very much development solar power system; if energy applied solar energy is as the electric power of tending to act of electrochemical treatment system; then the application surface of practice is wider, and the running cost of process regulation may be cheaper.Therefore, utilize solar panels to transfer sun power to electric energy in native system, have the function of voltage stabilizing with battery storage electric energy concurrently, directly export with direct current, provide electrochemical treatment systematic electricity originate, carry out the Degradation of the pollutions such as chlorinated organics in underground water.There is the improper disposal of many escape because of plant operation or harmful cause waste both at home and abroad, and cause groundwater pollution problem.Such as, chlorinated organics (the chloride aliphatic hydrocarbon such as trieline or zellon (Chlorinated Aliphatic Hydrocarbons; CAHs) be namely modal organic pollutant in underground water.Chlorinated organics because of its low water solubility and high boiling characteristic, and is classified as one of pollutent of the most difficult removal.Particularly when chlorinated organics is with DNAPLs (the DenseNonaqueous-Phase Liquid heavier than water; DNAPL) when source of pollution kenel is present in underground water, the degree of difficulty removing chlorinated organics more increases, and required time and cost are also difficult to estimate.
Soil groundwater pollutant, generally can be divided three classes according to the relation for the treatment of technology with process site.The first kind is existing (in-situ) treatment technology, refers to without excavation contaminated soil program, directly now to carry out the process of pollutent.Equations of The Second Kind is on-the-spot (on-site) process, namely directly processes at the scene after excavation procedure.3rd class is (ex-situ) process of leaving the theatre, and after namely excavating polluted soil, soil is transported out of process site and processes.
In underground water remedial technology, now treatment technology is because it is in the advantage in economic face and the low destructiveness to site, has high commercial potentiality and technical application.Wherein, for in underground water remedial technology, traditional regulation method is mainly to extract facture (Pump and Treat), and its shortcoming need extract excessive underground water for during process, but because of the nonuniformity of underground reservoir quality, some district pollution thing cannot pump-and-treat system smoothly.With physical property regulation engineering method, soil gas extracts method (Soil Vapor Extraction) and is extensively adopted.But soil gas extracts method and is only limitted to volatile matter in process soil, and the dusty gas of extraction still must process further again.In addition in conjunction with air Injection method (Air Sparging) although the volatile organic contaminant of soil and underground water can be processed simultaneously, but still be limited to soil property comparatively non-densified regions, for quality soil treatment poor effect closely.With chemical regulation engineering method, now chemical oxidization method (In Situ Chemical Oxidation) is very general in recent years, although the object of fast degradation underground pollution thing can be reached, due to chemical agent generally need be added as hydrogen peroxide (H
2o
2), sweet smell rises reagent (Fenton Reagent), persulphate medicament (Persulfate) etc., if therefore a large amount of interpolation is incured a considerable or great expense.Although and biological regulation method is considered to meet ecology most and effective treatment process, shortcoming is treatment time long (reaching several years), cannot practical requirement.
Electric power (Electrokinetics, EK) technology of educating is new in recent years emergence and extremely potential treatment process again, and its major advantage is: (1) can produce uniform osmosis stream in the soil media that heterogeneity is high and perviousness is low; (2) flow direction of osmosis stream can be controlled; (3) good to the removal efficiency of pollutent; (4) there is quite high economic benefit; (5) can integrate with other remedial technologies simultaneously use; And (6) pollutant type applicatory is very extensive.But current electrokinetics is applied to process heavy metal pollution of soil thing more, is applied to groundwater pollutant process very less, also without being applied to underground water regulation.Common processing mode is that electrode is put into contaminated soil and underground water at present, the pollutent in contaminated soil and underground water can be made after energising and because the pollutent in soil and underground water is attracted to ate electrode and adds medicament by the electricity principle that there is a natural attraction between the sexes, pollutent is dissolved in medicine, finally again the sewage containing soil and groundwater pollutant being evacuated to ground does sewage disposal, again gets back in system and circulate after sewage disposal is clean.
Summary of the invention
An object of the present invention is to provide a kind of electrolysis process now processing underground water, utilizes the electrolyzer of ad hoc structure to go deep into the pollutent degree of depth, contiguous pollutent scope, groundwater pollutant of directly now degrading.Another object is to provide a kind of electrolysis process now processing underground water, its have reduce processing cost, the anti-system of non-secondary pollution problem and to process site there is low destructive advantage.
Another object of the present invention is to provide a kind of electrolysis process now processing underground water, its electrolyzer used has and is convenient for carrying, easily stretch into the advantage in the responsing well of process site, it is applicable to the setting of the above well casing of 2 inch, and also without the restriction arranging the degree of depth.According to above-mentioned purpose of the present invention, a kind of electrolysis process now processing underground water is proposed.Now process in the electrolysis process of underground water in an embodiment, comprise the following steps.Electrolyzer is provided, provides power supply to give described electrolyzer, set the voltage of described power supply in a pre-determined range; And setting electrolytic reaction is in a set rate.
Further, described predetermined voltage is 2.5 volts to 5 volts.
Further, the resultant of electrolytic reaction contains chlorine.
Further, the electrolysis process now processing underground water further comprises and adds ionogen, to accelerate electrolytic reaction speed.
Further, described ionogen includes sodium sulfate (Na
2sO
4).
Further, electrolyzer comprises the first porous electrode pipe, the second porous electrode pipe, the first insulating part and the second insulating part.First porous electrode pipe has the first relative head and the first afterbody.Second porous electrode pipe to be arranged in the first porous electrode pipe and to have the second relative head and the second afterbody.First insulating part is arranged between the first head and the second head.Second insulating part is arranged between the first afterbody and the second afterbody.Arrange electrolyzer in the well casing of site, wherein the groundwater flow of site is through well casing.Carry out actuation step and drive electrolyzer process underground water, to produce electrolysis reaction to make the chlorinated organics of underground water.
One embodiment of the invention, above-mentioned chlorinated organics comprises trieline.According to one embodiment of the invention, when carrying out above-mentioned actuation step, do not add chemical agent in underground water.
According to one embodiment of the invention, the above-mentioned electrolysis process now processing underground water more comprises and utilizes electric supply installation to be electrically connected electrolyzer.
According to one embodiment of the invention, above-mentioned electric supply installation comprises solar power generation unit or battery.
According to one embodiment of the invention, the driving voltage of above-mentioned actuation step is 2.5 volts to 5 volts, and driving time is 100 minutes to 20 days.Further, described predetermined voltage is 2.5 volts, 3 volts, 4 volts to 5 volts.
According to one embodiment of the invention, the material of above-mentioned first porous electrode pipe comprises platinum, gold or platinum-ruthenium alloys.
According to one embodiment of the invention, the above-mentioned electrolysis process now processing underground water, wherein the material of the second porous electrode pipe comprises platinum, gold or platinum-ruthenium alloys.
According to one embodiment of the invention, between above-mentioned first porous electrode pipe and the second porous electrode pipe, there is distance, and distance is 0.3 centimeter to 0.5 centimeter.
According to one embodiment of the invention, above-mentioned first insulating part also comprises insulation division and protection portion.Insulation division is arranged between the first head and the second head.Protection portion connects insulation division, and protection portion is covered on the first head and on the second head.
The electrolysis process now processing underground water of the present invention utilizes the electrolyzer of ad hoc structure to process the site of polluting by chlorinated organics, and directly carries out now processing to chlorinated organics in well casing.Wherein, the electrolyzer that the electrolysis process now processing underground water of the present invention uses can go deep into the pollutent degree of depth, contiguous existing ground contamination thing scope, groundwater pollutant of directly degrading.Therefore, the electrolysis process now processing underground water of the present invention must not extract polluted underground water out floor treatment, can reduce processing cost.In addition, the electrolysis process now processing underground water of the present invention optionally can add the chemical agent (as catalyzer, reagent or ionogen etc.) be applicable to, to accelerate process and the time of electrolysis.
In addition, of the present inventionly now to process in the electrolysis process of underground water, its electrolyzer used is the modularized electrolyzer comprising two insulating parts and two porous electrode pipes, device volume is little and light and handy, therefore have and be convenient for carrying, easily stretch into the advantage in the responsing well of process site, and be applicable to the setting of the above well casing of 2 inch, also without the restriction arranging the degree of depth.
Accompanying drawing explanation
For above and other object of the present invention, feature, advantage and embodiment can be become apparent, being described as follows of institute's accompanying drawings:
Fig. 1 illustrates a kind of schema now processing the electrolysis process of underground water according to one embodiment of the invention.
Fig. 2 A illustrates the diagrammatic cross-section of the electrolyzer that a kind of electrolysis process now processing underground water according to one embodiment of the invention uses.
Fig. 2 B illustrates that electrolyzer that a kind of electrolysis process now processing underground water according to one embodiment of the invention uses is arranged at the diagrammatic cross-section of site.
Fig. 3 A is under the concentration of fixing sodium sulfate is 0.002M, the ratio time history plot of trieline.
Fig. 3 B is under fixing input voltage is 3 volts, the ratio time history plot of trieline.
Fig. 3 C is the ratio time history plot of the trieline of underground water.
Fig. 3 D is the histogram of the concentration changes with time of the trieline of the underground water of upstream well casing and downstream well casing.
Fig. 4 under difference determines voltage conditions in 0.002M electrolytic solution (Na
2sO
4) in the degraded situation of TCE.
Fig. 5 is in 0.002M electrolytic solution (Na
2sO
4) the middle different TCE first-order degradation reaction determining voltage.
Fig. 6 determines the degraded situation of potential electrolysis TCE under different electrolyte concentration condition with 3V.
Fig. 7 determines potential electrolysis with 3V and reacts in the TCE first-order degradation of different electrolyte concentration.
Fig. 8 show TCE along with time variations produce the reaction of degraded.
Description of reference numerals
100 methods
110,120,130 steps
200 electrolyzers
210 first porous electrode pipes
210a first head
210b first afterbody
220 second porous electrode pipes
220a second head
220b second afterbody
230 first insulating parts
231 insulation divisions
232 protection portion
232a bores a hole
232b chamfering structure
240 second insulating parts
The 250 insulation collars
260 first electric wires
270 second electric wires
280 electric supply installations
Embodiment
Below coordinate embodiments of the invention describe in detail technology contents of the present invention, structural attitude, institute reach object and effect.The medicine used in the embodiment of the present invention comprises sodium sulfate (European PANREACChemicals, analyze reagent level, purity 99.00%), sodium-chlor (Sigma-Aldrich, analyze reagent level, purity 99.00%), ultra-high purity nitrogen gas (bright and beautiful moral gas, 99.999%), air originates from Swan oil-free compressor.Solution needed for experiment is all prepared with two sections of water (resistance value reaches 18.0M Ω-㎝), and two sections of water are taken from Milli-Q system (Millipore, Tk-10, USA).
The present invention is in conjunction with solar powered with electrochemical treatment technology, and the solar power electrolytic system proposed configures, and unit comprises the elements such as solar panels, transmodulator, battery, bipolar electrode treatment system.System and device used in the present invention mainly comprises solar power system and electrolytic treatment system two parts: (1) solar power system adopts 2 100W solar panels, estimate peak voltage 25.38 volts, 7.89 amperes, electric current, tool frequency transformer, buck potentiostat, store battery are equipped with, and carry out the control of AC/DC output voltage/electric current with MPU.(2) electrolytic treatment system adopts Nonseparation 4 aperture reactive tank, its volume is 1L, 4 apertures are arranged at reactive tank top, for the purposes such as working electrode and supporting electrode is installed, gas explosion relief, thief hatch, 4 apertures all seal, the external gas production bag of gas explosion relief can synchronous collection gaseous sample, and reaction tank bottom stirs with magnetite avoids bubble to accumulate on electrode surface.Two pole formula electrodes are all designed to three central column platinum titanium mesh electrodes, three central column electrode length 12cm, working electrode is composed in parallel by diameter 8cm, 6cm, 4cm tri-4 μm of platinum titanium mesh, supporting electrode is composed in parallel by diameter 7cm, 5cm, 3cm tri-4 μm of platinum titanium mesh, and supporting electrode directly can enter working electrode by down, interelectrode distance is 1cm only, and with iron not actor playing a supporting role's ring fix, avoid electrode contact to cause short circuit.
Operating method
Preparation TCE concentration 0.5 to 20mg/L solution simulation contaminated underground water, adds a small amount of Na
2sO
4as supporting electrolyte, operation adopts determines potential electrolysis, working electrode potential is controlled by solar energy regulator, the change of reactor voltage and electric current in parallel and series connection avometer measurement process again, often group tests the reaction times with 360min or 480min for principle, in the process of carrying out every 0,5,15,30,60,180,360,420 and 480min sampling once, the TCE concentration that the sample gathered utilizes gas chromatograph analysis residual, and confirm that TCE degradation process generates the situation of intermediate product.
Sample analysis method
With the sampling of closed acquisition mode in process, insert in electrolyzer with 20cc Glass syringe cylinder and extract electrolysis water sample, 100 μ L collected specimens are added in the salt solution of 25%, with the solubleness in salting-out process reduction water to disengage organism.Solid-phase microextraction (SPME) mode is utilized to carry out sample pre-treatments, by GERSTEL MPS2 automatic sample handling system sample introduction, with engine room in the Fiber insertion of SUPELCO 100 μm, with Head space headspace absorption 20min at 32 DEG C, desorption 5min under the vaporizing tube of 250 DEG C, with current-carrying gas nitrogen (N
2) import in chromatography tubing string and analyze.On sample, machine carries out the analysis of sample TCE concentration quantitative with gas chromatograph/micro-electron capture detector (GC/ μ ECD), GC type is Agilent 6890N, its temperature parameter Inlet:230 DEG C, detector: 250 DEG C, tubing string: Agilent DB-624 (30.0m, 320 μm, 1.80 μm), flow velocity: 1mL/min, heating up 35 DEG C stops 4.0min, 100 DEG C are warming up to 5 DEG C/min, be warming up to 220 DEG C with 30 DEG C/min again, finally stop 1min.Detector μ ECD has high sensitivity for organism halogen-containing in water, the species of Main Analysis have VC, DCE, DCM, Tra-DCE, Cis-DCE, TCE, PCE, analyze to impose a condition learn that the residence time of various chlorine-containing compound is about DCE:8.10min, DCM:9.22min, Tra-DCE:9.87min, Cis-DCE:12.07min, TCE:15.42min, PCE:18.83min according to GC/ μ ECD.Blank water sample analysis is first released into, to guarantee that plant and instrument interference drops to minimum before sample analysis; And operative norm product check the calibration accuracy of analysis confirmation calibration curve, perform checking of calibration curve after every 10 sample analysis, after completing sample analysis, perform checking of calibration curve again.
Result and discussion
Inquire into the impact that different operating voltage is degraded on TCE
This research preparation TCE concentration 10mg/L solution carries out electrolytic experiment, for confirming TCE degraded dechlorination effect, supporting electrolyte is avoided selecting KCl, another for meet underground water present situation as far as possible, even if adopt extremely low electrolyte concentration that electrolytic reaction efficiency can be caused poor, therefore select 0.002M Na
2sO
4electrolyte concentration, as experiment condition, carries out the different comparison determined voltage parameter and affect TCE degraded.Experimental result finds, operating voltage 2.5V, 3V and 4V electrolysis 4 hours, and the remaining rate of trieline is only 2%, 1% and 1%, as shown in Figure 2.Operating voltage controls at more than 2.5V, can be almost degradable by trieline in reactor, and major cause may to trigger the OH free radical generated relevant with electrochemistry.More than operating voltage 2.5V can start S
2o
8 2-/ SO
4 2-the generation of redox matchmaker, then pass through S
2o
8 2-/ SO
4 2-the sub-water of decomposition of redox matchmaker forms OH free radical, makes it carry out indirect oxidation degraded TCE, as shown in reaction formula (3.1) and (3.2).Operating voltage controls at more than 3V, can generate OH free radical, as shown in reaction formula (3.3) by Direct Electrolysis water.
2SO
4 2－→S
2O
8 2－+2e
－(3.1)
SO
4 －·+H
2O→OH·+SO
4 2－+H
+(3.2)
H
2O→OH·+H
++e
－(3.3)
Please refer to the 1st figure, Fig. 1 and show a kind of schema now processing the electrolysis process 100 of underground water according to one embodiment of the invention.In an example, the electrolysis process 100 now processing underground water is applicable to process the site of polluting by chlorinated organics.In an illustrative example, chlorinated organics comprises trieline.
Please with reference to Fig. 1 and Fig. 2 A.Fig. 2 A illustrates the diagrammatic cross-section of the electrolyzer 200 that a kind of electrolysis process 100 now processing underground water according to one embodiment of the invention uses.In the method 100, step 110 provides electrolyzer 200.Electrolyzer 200 comprises the first porous electrode pipe 210, second porous electrode pipe 220, first insulating part 230 and the second insulating part 240.As shown in Figure 2 A, the first porous electrode pipe 210 has the first head 210a and the first afterbody 210b, and the first afterbody 210b and the position of the first head 210a are positioned at relative two ends of the first porous electrode pipe 210.In an example, the length of the first porous electrode pipe 210 is about 1 meter.Be provided with many micropores in first porous electrode pipe 210, and the mean pore size of these micropores can be rough 4 microns.In another example, the first porous electrode pipe 210 overall appearance is slightly cylindrical.
In an example, the first porous electrode pipe 210 can be porous electrocatalysis noble electrode pipe, that is when electrolyzer 200 carries out electrolysis procedure, therefore the first porous electrode pipe 210 can not be consumed.In an illustrative example, the material of the first porous electrode pipe 210 can comprise platinum, gold or platinum-ruthenium alloys.Wherein, in order to save material cost and there is electrocatalysis effect when electrolysis procedure, the first porous electrode pipe 210 can on the plated surface of POROUS TITANIUM webmaster platinum, gold or platinum-ruthenium alloys, to form porous electrocatalysis noble electrode pipe.
As shown in Figure 2 A, the second porous electrode pipe 220 has the second head 220a and the second afterbody 220b, and the second afterbody 220b and the position of the second head 220a are positioned at relative two ends of the second porous electrode pipe 220.In an example, the length of the second porous electrode pipe 220 is about 1 meter.Be provided with many micropores equally in second porous electrode pipe 220, and the mean pore size of these micropores can be rough 4 microns.In another example, the second porous electrode pipe 220 overall appearance is slightly cylindrical.In addition, the second porous electrode pipe 220 is arranged in the first porous electrode pipe 210.In an illustrative example, the nozzle diameter of the first porous electrode pipe 210 is about 42 millimeters, and the nozzle diameter of the second porous electrode pipe 220 is about 35 millimeters.Nozzle diameter due to the second porous electrode pipe 220 is less than the first porous electrode pipe 210, so the second porous electrode pipe 220 can be arranged in the first porous electrode pipe 210.
In an example, the second porous electrode pipe 220 can be porous electrocatalysis noble electrode pipe, that is when electrolyzer 200 carries out electrolysis procedure, therefore the second porous electrode pipe 220 can not be consumed.In an illustrative example, the material of the second porous electrode pipe 220 can comprise platinum, gold or platinum-ruthenium alloys.Wherein, in order to save material cost and there is electrocatalysis effect when electrolysis procedure, the second porous electrode pipe 220 can on the plated surface of POROUS TITANIUM webmaster platinum, gold or platinum-ruthenium alloys, to form porous electrocatalysis noble electrode pipe.
As shown in Figure 2 A, the first insulating part 230 is arranged between the first head 210a and the second head 220a, and the second insulating part 240 is arranged between the first afterbody 210b and the second afterbody 220b.In an example, the material of the first insulating part 230 or the second insulating part 240 can comprise tetrafluoroethylene (being commonly called as Teflon).First insulating part 230 and the second insulating part 240 at least have multi-effect, describe in detail as after.
First, as shown in Figure 2 A, because the second porous electrode pipe 220 is arranged in the first porous electrode pipe 210, and the first head 210a of the contiguous first porous electrode pipe 210 of the second head 220a of the second porous electrode pipe 220, the first afterbody 210b of the contiguous first porous electrode pipe 210 of the second afterbody 220b of the second porous electrode pipe 220.Therefore, when the first insulating part 230 is arranged between the first head 210a and the second head 220a, and the second insulating part 240 is when being arranged between the first afterbody 210b and the second afterbody 220b, first insulating part 230 and the second insulating part 240 are in two ends end to end of the first porous electrode pipe 210 and the second porous electrode pipe 220 respectively, therefore the intermediate ends of the first porous electrode pipe 210 and the intermediate ends of the second porous electrode pipe 220 can not contact with each other, and avoid direct electric connection the mutually of the first porous electrode pipe 210 and the second porous electrode pipe 220 and cause short circuit.In an example, in order to reinforced insulation effect, electrolyzer 200 comprises multiple insulation collar 250, and these insulation collars 250 are arranged between the intermediate ends of the first porous electrode pipe 210 and the intermediate ends of the second porous electrode pipe 220.
In addition, the first insulating part 230 and the second insulating part 240 also can be used to the distance between control first porous electrode pipe 210 and the second porous electrode pipe 220.In general, because the first insulating part 230 is arranged between the first head 210a and the second head 220a, and the second insulating part 240 is arranged between the first afterbody 210b and the second afterbody 220b.So, the thickness of the first insulating part 230 and the second insulating part 240 by and distance between the first porous electrode pipe 210 and the second porous electrode pipe 220 there is positively related relation.In an example, the thickness of the first insulating part 230 and the second insulating part 240 generally at 0.3 centimeter to 0.5 centimeter, to make the distance between the first porous electrode pipe 210 and the second porous electrode pipe 220 also rough at 0.3 centimeter to 0.5 centimeter.Generally, when the first porous electrode pipe 210 and the second porous electrode pipe 220 distance more hour, then the electrolysis effectiveness of electrolyzer 200 is better.But when the distance of the first porous electrode pipe 210 and the second porous electrode pipe 220 is less than 0.3 centimeter, then the tolerance of each component of electrolyzer 200 is too small and not easily make.On the other hand, if the distance of the first porous electrode pipe 210 and the second porous electrode pipe 220 is greater than 0.5 centimeter, then electrolysis effectiveness step-down, and the size of electrolyzer 200 will be caused simultaneously to become large, and create not portable or not easily now process the shortcoming of groundwater pollutant at small size responsing well.
As shown in 2A figure, in an example, the first insulating part 230 can comprise insulation division 231 and protection portion 232.Insulation division 231 is arranged between the first head 210a and the second head 220a.Insulation division 231 mainly can be used to the direct electric connection avoiding the first porous electrode pipe 210 and the second porous electrode pipe 220, and can be used to the distance between control first porous electrode pipe 210 and the second porous electrode pipe 220.Protection portion 232 connects insulation division 231.In an example, protection portion 232 is slightly in cylinder shape, and protection portion 232 has chamfering structure 232b away from the first head 210a and the second head 220a part, and person easy to use carries gripping.In another example, the diameter of protection portion 232 is identical or slightly larger than the nozzle diameter of the first porous electrode pipe 210.Protection portion 232 can be used to protection first head 210a and the second head 220a, impaired to avoid the first head 210a and the second head 220a to be collided.
Please refer to Fig. 2 B, Fig. 2 B shows the diagrammatic cross-section that electrolyzer 200 that a kind of electrolysis process 100 now processing underground water according to one embodiment of the invention uses is arranged at site 900.Generally, electrolyzer 200 needs just can carry out electrolysis procedure with electric power as the energy.In an example, the first porous electrode pipe 210 is electrically connected with one end of the first electric wire 260, the other end of the first electric wire 260 is electrically connected electric supply installation 280, and the other end electric connection electric supply installation 280 of the second porous electrode pipe 220, second electric wire 270 is electrically connected with one end of the second electric wire 270.In an example; as shown in 2A figure; because the second porous electrode pipe 220 is in the first porous electrode pipe 210; therefore can pass through and establish perforation 232a at protection portion 232 cutter, make the second electric wire 270 be electrically connected with the second porous electrode pipe 220 being arranged in the first porous electrode pipe 210 by perforation 232a thus.In another example, electric supply installation 280 comprises solar power generation unit or battery.In an illustrative example, the electric energy that solar power generation unit produces through sunlight can be stored in battery, more battery-poweredly gives electrolyzer 200.
Referring again to Fig. 1 and Fig. 2 B, electrolyzer 200 is arranged in the well casing 910 of site 900 by step 120, and wherein the underground water 920 of site 900 flows through well casing 910.In an example, under electrolyzer 200 entirety is immersed in the liquid level of underground water 920.After carry out step 120, carry out actuation step 130, drive electrolyzer 200 to process underground water 920 thus.Wherein, electrolyzer 200 can produce electrolysis with the chlorinated organics of underground water 920 and react.In an example, if the chlorinated organics of underground water 920 is trieline, the product after electrolytic reaction is chlorion, hydrogen ion, carbonic acid gas and water.In other words, the pollutent of trieline, after electrolytic reaction, forms carbonic acid gas and the water of environmental sound.In an example, the driving voltage used in actuation step 130 is 2.5 volts to 5 volts and driving time is 100 minutes to 20 days.
In an example, now process in the actuation step 130 of the electrolysis process 100 of underground water 920, also can add eliminating and add chemical agent in the experiment of underground water 920.This now processes the electrolysis process 100 of underground water when adding additional chemical medicament (as catalyzer, reagent or ionogen etc.), still can have and the chlorinated organics of underground water 900 is produced electrolysis the effect of reaction.Therefore, now process the problem of the anti-system of electrolysis process 100 non-secondary pollution of underground water, and to process site 900, there is low destructive advantage.
In the electrolysis process 100 now processing underground water 920, utilize the electrolyzer 200 of ad hoc structure to process the site 900 of polluting by chlorinated organics, and directly carry out now processing to chlorinated organics in well casing 910.The electrolyzer 200 used is the modularized electrolyzer comprising two insulating parts (i.e. the first insulating part 230 and the second insulating part 240) and two porous electrode pipes (i.e. the first porous electrode pipe 210 and the second porous electrode pipe 220), therefore have and be convenient for carrying, easily stretch into the advantage in the reaction well casing 910 of process site 900.In addition, electrolyzer 200 is applicable to the setting of the above well casing 910 of 2 inch, and also without the restriction arranging the degree of depth.Wherein, the electrolyzer 200 that the electrolysis process 100 now processing underground water 920 uses can go deep into the pollutent degree of depth, contiguous existing ground contamination thing scope, the chlorinated organics of underground water 920 of directly degrading.Therefore, the electrolysis process 100 now processing underground water 920 must not extract underground 920 water out floor treatment, can reduce processing cost.
Below enumerate examples of implementation, prove the electrolysis process processing underground water of the embodiment of the present invention thus existingly, really have and process and the effect of chlorinated organics of degrading.
Before the test carrying out embodiment, first need confirm the effect of electrolyzer electrolysis.First, in pure water, add sodium sulfate and trieline, to form test fluid.The concentration of trieline is 10 mg/litre to 13 mg/litre.Sodium sulfate is mainly used as ionogen, therefore can use lower concentration.Then, provide electrolyzer, the detailed construction of electrolyzer in earlier paragraphs introduction, therefore repeats no more.Then, under the concentration of fixing sodium sulfate is 0.002M, carries out different input voltage (being respectively 2.5 volts, 3 volts and 4 volts) tests, and under fixing input voltage is 3 volts, carries out concentration (being respectively 0.002M, 0.1M and 0.5M) test of different sodium sulfate.Please refer to Fig. 3 A and Fig. 3 B, Fig. 3 A is under the concentration of fixing sodium sulfate is 0.002M, the ratio time history plot of trieline, and 3B figure is under fixing input voltage is 3 volts, the ratio time history plot of trieline.As shown in 3A and 3B figure, all can by the ratio electrolysis of trieline in water to less than 20% of original content in 100 minutes, and when the concentration of voltage or sodium sulfate is higher, electrolytic efficiency is higher.In addition, when after 300 minutes, in water, trieline is removed by complete electrolysis.
After determining that electrolyzer possesses the effect of electrolysis trieline, then test with the actual underground water (concentration of trieline is 250 micrograms per litre) being subject to trieline pollution further.When carrying out test underground water, directly electrolyzer being arranged in underground water, wherein not needing to add sodium sulfate in underground water, this is because underground water itself is containing microelectrolysis matter, therefore without the need to adding sodium sulfate as electrolytical purposes.Afterwards, carry out actuation step, this actuation step uses 3 volts, 4 volts to test respectively with the voltage of 5 volts.The result of gained please refer to Fig. 3 C, and Fig. 3 C is the ratio time history plot of the trieline of underground water.From Fig. 3 C, the ratio of the trieline of underground water reduces gradually along with the increase in treatment time.Wherein, when the voltage used is respectively 3 volts, the time approximately passing through 60 minutes can remove 45% trieline, if when the voltage used is respectively 4 volts or 5 volts, the time approximately passing through 60 minutes can remove 70% trieline.As can be seen here, electrolyzer really can the trieline of electrolysis underground water.
After above-mentioned test, determine that electrolyzer can trieline in electrolysis underground water.Then, then certain trieline pollued field selected, and be arranged at by electrolyzer in the upstream well casing of site, the degree of depth that arranges of electrolyzer is 10 meters, and carries out the test of about 20 days with the voltage driven electrolyzer of 3 volts.Wherein, except measuring the trieline concentration in the well casing of upstream, also synchronously measure the trieline concentration of downstream well casing.Please refer to Fig. 3 D, Fig. 3 D is the histogram of the concentration changes with time of the trieline of the underground water of upstream well casing and downstream well casing.As can be known from the results, along with the increase of electrolysis time, the trieline concentration of the underground water of upstream well casing and downstream well casing all reduces.As can be seen here, the electrolysis process processing underground water of the embodiment of the present invention, has and processes and the effect of chlorinated organics of degrading existingly really.
For cooperatively interacting between two in science and practice, the following description then supports practice feasibility of the present invention with experimental data.
Fig. 4 shows the TCE first-order degradation speed of reaction of operating voltage 2.5V, 3V and 4V, and data are in ln (C
0/ C) present good linear relationship (R2>0.9) in vs.t figure, display TCE DeR meets first kernel response power, the DeR speed of voltage 3V and 4V is suitable, all a little more than the DeR speed of voltage 2.5V, major cause is that more than operating voltage 3V can generate OH free radical by Direct Electrolysis water, thus accelerates TCE DeR speed.
Fig. 6 inquires into the impact that different electrolyte concentration is degraded on TCE.
For understanding the impact that different electrolyte concentration is degraded on TCE, 0.5M, 0.1M, 0.002MNa are prepared
2sO
4electrolyte concentration carries out electrolytic experiment, adopts and determines the operational condition electrolysis 360min of voltage 3V, and adds blank assay and compare.
Show blank assay for want of ionogen transmission electronics in figure, TCE degradation efficiency is poor only reaches 16%, and other experiments group TCE degradation efficiency all can reach more than 99%.Wherein best with the TCE degradation efficiency of 0.5M electrolyte concentration experimental group, in 30min, reached that can to reach TCE in 95%, 360min degradable.The comparative result of different electrolyte concentration meets expection, adds the carrying out that high density ionogen is conducive to electrolysis oxidation-reduction reaction in reactor, even if electrolyte concentration is down to 0.002M, also can obtain satisfied TCE degradation efficiency.
0.5M, 0.1M, 0.002M Na is shown in figure
2sO
4the TCE first-order degradation speed of reaction of electrolyte concentration, except blank assay, other group experimental datas present good linear relationship (R2>0.86) in ln (C0/C) vs.t figure, display TCE DeR meets first kernel response power, and first kernel response speed increases along with electrolyte concentration and increases.In low electrolyte concentration 0.002M Na
2sO
4in solution, determine potential electrolysis operation with 3V, comparatively approximate underground water its natural environment, the first kernel response speed of TCE degraded is about 0.02min-1.
Fig. 7 determines potential electrolysis with 3V and reacts in the TCE first-order degradation of different electrolyte concentration.
The product inquired in TCE degradation process generates
General biological degradation TCE mechanism, can generate vinylchlorid by reduction dechlorination, every More TCE degraded can discharge 2 More's chlorions, and reduction dechlorination rate is 67%.The sample that the present invention gathers in electrolytic process, except analysis TCE concentration, also utilizes the chlorine ion concentration of ion chromatograph analytic sample simultaneously.If the complete reduction dechlorination of TCE, every More TCE degraded can discharge 3 More's chlorions, and the chlorine ion concentration therefore recorded is converted to reduction dechlorination rate, in order to the mass balance calculation$ carrying out chlorion.The degradation rate that Fig. 5 shows experiment end of a period TCE is close in 100%, and the TCE reduction dechlorination rate of chlorion T.G Grammar is 91%, and the error of general analysis data, between 10% ~ 15%, therefore can be considered the complete dechlorination of TCE.
Sample GC/ μ ECD analysis is also synchronous to be detected for TCE intermediates VC, DCE, DCM, Tra-DCE, Cis-DCE, but does not all record the intermediate product of any TCE degraded, on the other hand via the aerogenesis collecting reactor, with CO
2gas detecting machine can record CO
2generation, obtain the evidence of trieline by electrolytic mechanism mineralising.If TCE permineralization, every More TCE degraded can generate 2 More CO
2, the CO therefore recorded
2concentration is converted to mineralization rate, in order to the mass balance calculation$ carrying out carbon atom.The degradation rate showing experiment end of a period TCE in figure is close in 100%, CO
2the TCE mineralization rate of T.G Grammar is 88%, still in general rational experimental analysis data error scope, therefore can be considered TCE permineralization.Reaction formula (3.4) is the Theoretical Equilibrium reaction formula according to the complete dechlorination of TCE and permineralization hypothesis, electrolysis TCE has and produces hydrogen effect, and experiment end of a period pH value of solution has and significantly declines, pH value of solution before the present invention's research records electrolytic experiment be 6.28 and electrolytic experiment after pH value of solution be 3.76, also supporting can by the argument of complete for TCE dechlorination and permineralization by electrochemical reaction mechanism.Following chemical formula then describes above-mentioned argument:
C
2HCl
3+4H
2O→2CO
2+3Cl
-+ (3.4)
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. process the electrolysis process containing source of pollution underground water now, it is characterized in that, comprise the following steps:
One electrolyzer is provided;
Power supply is provided to give described electrolyzer;
Set the voltage of described power supply in a pre-determined range; And
Setting electrolytic reaction is in a set rate.
2. the electrolysis process now processed containing source of pollution underground water according to claim 1, is characterized in that, the material of described electrolyzer comprises platinum, gold or platinum-ruthenium alloys.
3. the electrolysis process now processed containing source of pollution underground water according to claim 1 and 2, is characterized in that, described power supply comprises a solar power generation unit or a battery.
4. the electrolysis process now processing underground water according to claim 1, is characterized in that, predetermined voltage is 2.5 volts to 5 volts.
5. the electrolysis process now processing underground water according to claim 4, is characterized in that, described predetermined voltage is 2.5 volts, 3 volts, 4 volts to 5 volts.
6. the electrolysis process now processing underground water according to claim 1, is characterized in that, the resultant of electrolytic reaction contains chlorine.
7. the electrolysis process now processing underground water according to claim 1, is characterized in that, further comprises and add ionogen, to accelerate electrolytic reaction speed.
8. the electrolysis process now processing underground water according to claim 2,4 or 6, is characterized in that, further comprises and add ionogen, to accelerate electrolytic reaction speed.
9. the electrolysis process now processing underground water according to claim 7, is characterized in that, described ionogen includes sodium sulfate (Na
2sO
4).
10. the electrolysis process now processing underground water according to claim 8, is characterized in that, described ionogen includes sodium sulfate (Na
2sO
4).
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| CN107324450A (en) * | 2016-04-29 | 2017-11-07 | 昆山科技大学 | Packing type ground water circulation is electrolysed regulation system |
| CN108408992A (en) * | 2018-01-25 | 2018-08-17 | 中国地质大学（武汉） | A kind of regulation and control method in situ of water-bearing layer Redox Condition |
| CN108956217A (en) * | 2018-09-28 | 2018-12-07 | 四川省天晟源环保股份有限公司 | A kind of novel SOIL GAS collection and detection device |
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| CN101362610A (en) * | 2008-08-25 | 2009-02-11 | 浙江大学 | Method for removing methane chlorides in water or waste water by electrolysis |
| CN101466874A (en) * | 2006-06-13 | 2009-06-24 | 氧合水技术股份有限公司 | Water treatment system |
| CN203653309U (en) * | 2013-12-31 | 2014-06-18 | 武汉大学 | Solar power driven chlorinated organic compound polluted underground water restoring device |
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| CN101466874A (en) * | 2006-06-13 | 2009-06-24 | 氧合水技术股份有限公司 | Water treatment system |
| CN101362610A (en) * | 2008-08-25 | 2009-02-11 | 浙江大学 | Method for removing methane chlorides in water or waste water by electrolysis |
| CN203653309U (en) * | 2013-12-31 | 2014-06-18 | 武汉大学 | Solar power driven chlorinated organic compound polluted underground water restoring device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107324450A (en) * | 2016-04-29 | 2017-11-07 | 昆山科技大学 | Packing type ground water circulation is electrolysed regulation system |
| CN108408992A (en) * | 2018-01-25 | 2018-08-17 | 中国地质大学（武汉） | A kind of regulation and control method in situ of water-bearing layer Redox Condition |
| CN108956217A (en) * | 2018-09-28 | 2018-12-07 | 四川省天晟源环保股份有限公司 | A kind of novel SOIL GAS collection and detection device |
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