CN104016531A - Underground water restoration method by iron anode coupled palladium catalytic hydrogenation - Google Patents
Underground water restoration method by iron anode coupled palladium catalytic hydrogenation Download PDFInfo
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Abstract
The invention relates to an underground water restoration method by iron anode coupled palladium catalytic hydrogenation. According to the method, an electrochemical technique is combined with palladium catalytic hydrogenation reduction according to the characteristics of underground water and the parameter requirements of the palladium catalytic hydrogenation reduction technique, i.e. an iron anode pretreatment unit is utilized to remove reduced-state sulfur, calcium/magnesium ions and the like capable of influencing the palladium catalytic reduction efficiency in the underground water, and meanwhile, hydrogen required by the palladium catalytic hydrogenation reduction is continuously generated, thereby enhancing the chemical reduction efficiency for pollutants. The method does not need exogenous hydrogen, thereby avoiding the problem of transportation and storage of abundant exogenous hydrogen. The method has the characteristics of high treatment efficiency, short treatment time, flexible operation, simple maintenance, high automation degree, environment friendliness and the like, and thus, is a green, practical, economic and safe underground water pollution restoration technique.
Description
Technical field
The invention belongs to Polluted Groundwater recovery technique field.The underground water restorative procedure that is specially a kind of iron anode coupling palladium shortening, is specially adapted to the reparation of the vattability species contaminated site underground water such as chlorinatedorganic, nitro-compound.
Background technology
Current China groundwater pollution situation is very severe, according to the initial investigation results of < < whole nation pollution prevention plan (2010 – the year two thousand twenty) > >, show, China's 90% urban groundwater suffers the pollution of toxic pollutant in various degree.
Traditional underground water recovery technique has Pump-and-Treat system, steam extraction process, biological restoration, permeable reactive barrier technology and in situ chemical oxidation technology etc., and they all have certain limitation in actual applications.Palladium catalytic hydrogenating reduction technology, in the Qi developed country rise nineties in last century, is repaired rapidly and efficiently, gets final product the organic reaction of deoxygenization chlorination in several minutes, and shortening effect is thorough and by product is less, is an important chemical reduction recovery technique.But the method also comes with some shortcomings: as 1. hydrogen supply is difficult.The reductive agent hydrogen that palladium catalytic hydrogenating reduction is used is supplied with by compression hydrogen, and need to increase hydrogen and dissolve mixing equipment, and the inflammable and explosive characteristic of hydrogen, increased accumulating risk.2. palladium catalyst poisoning and deactivation.In underground water, many materials can reduce rate of reduction, and particularly reduced sulfur wherein can cause palladium catalyst poisoning and lose activity.3. palladium catalysis is expensive, in order to extend its work-ing life, common way is regularly to use strong oxidizer to regenerate to palladium catalyst at present, but regenerative process inevitably can cause the loss of palladium content, and activity recovery completely, regenerative process has also strengthened difficulty and the cost of system operational management.These problems make the actual site remediation application of palladium catalytic reduction technology also fewer.
Summary of the invention
The present invention seeks to the deficiency existing in order to solve prior art, and a kind of original position supply and the catalyst deactivation difficult problem that can effectively solve hydrogen in underground water palladium catalytic hydrogenating reduction process is provided, and easy to operate, safeguard simple, the good and eco-friendly iron anode of the treatment effect palladium shortening underground water restorative procedure that is coupled.
For achieving the above object, the technical scheme that the present invention takes is: provide a kind of underground water restorative procedure of iron anode coupling palladium shortening, operation as follows:
Step (1), prepare a set of underground water prosthetic device that carries out iron anode coupling palladium shortening, comprise iron anode pretreatment unit, sand filtration unit and palladium catalyzed reaction unit, three unit connect by pipeline;
Step (2), iron anode pretreatment unit is installed, iron anode pretreatment unit comprises a water receptacle, water receptacle is provided with groundwater intake and first step water outlet, and anodic-cathodic is installed in water receptacle, along Groundwater flow path direction, anode I, negative electrode, iron anode is installed successively; In water receptacle, groundwater intake one side cross section is first installed anode I, and anode I selects titanium coating class inactive, conductive material to make, and negative electrode selects stainless steel plate or titanium coating electro-conductive material to make; Iron anode selects common iron material to make; Three electrodes all adopt plate electrode netted or that be evenly with holes, are conducive to water flow and improve current efficiency; At outer setting water pump and the direct supply of water receptacle, adopt water pump that underground water is pumped in water receptacle, by the direct supply of peripheral hardware, to three electrodes of yin, yang, provide electric current, and control by the current ratio of iron anode and anode I;
Step (3), sand filtration unit is installed, described sand filtration unit is connected between iron anode pretreatment unit and palladium catalyzed reaction unit, sand filtration unit comprises a sand filtration container, be provided with the sand filtration container water-in and the second stage water outlet that are connected with palladium catalyzed reaction unit with iron anode pretreatment unit, filler particles filtrate in sand filtration container, the iron throw out that sand filtration container produces for filtering iron anode pretreatment unit and the particulate matter of underground water;
Step (4), palladium catalyzed reaction unit is installed, described palladium catalyzed reaction unit comprises a catalyticreactor, the reactor water-in being connected with second stage water outlet is established in bottom, top is provided with treated water outlet, select the solid palladium granules of catalyst that diameter 1.5～5.0mm and palladium mass content are 0.5%～5%, and the granulated glass sphere that mixes diameter 2～4mm is filled in reactor, make to fill rear porosity 0.35～0.5;
Step (5), connect the pipeline of three unit; Start mounted device and carry out underground water reparation: by water pump, extract polluted underground water, switch on power simultaneously; The underground water polluting is introduced into iron anode pretreatment unit, flows through successively anode I, negative electrode, iron anode, then by sand filtration unit, finally enters palladium catalyzed reaction unit and react removal pollutent;
The underground water polluting is by anode I, and anode I, for generation of hydrogen ion and oxygen, has small portion reduced sulfur in the oxidation of anode I in the underground water of pollution, and underground water enters negative electrode and iron anode region subsequently, and negative electrode is for generation of hydroxide ion and hydrogen; The hydrogen constantly producing at this region negative electrode makes the saturated dissolved hydrogen of underground water, iron anode is for generation of ferrous ion, the hydroxide radical that ferrous ion produces with negative electrode is rapidly combined and is generated ferrous hydroxide, and ferrous hydroxide generates ironic hydroxide throw out by the oxygen reduction producing from anode I; Ironic hydroxide throw out is for reduced sulfur, calcium magnesium hardness and the part microorganism of removing underground water, for the reaction of follow-up palladium catalyst provides good environment;
The underground water polluting is flowed out and is entered sand filtration unit by first step water outlet after iron anode pretreatment unit, and underground water now also remainder iron throw out is held back by the granule filter material of filling in sand filtration container; Remove material poisonous to palladium catalyst in underground water, and in underground water, dissolved in hydrogen;
Behind sand filtration unit, when underground water flows into palladium catalyzed reaction unit from second stage water outlet, solubilised state hydrogen is removed underground water pollutant reduction efficiently under palladium katalysis, and the water after processing flows out from treated water outlet;
Step (6), monitoring processes organic concentration height in after purification water out, according to underground water repairing effect, carries out energy optimization, adopts feed water flow speed is regulated, or total current is regulated to optimization energy consumption.
Iron anode pretreatment unit, sand filtration unit and palladium catalyzed reaction unit in the step device that (1) described underground water is repaired in the present invention, three unit are indispensable, and are linked in sequence.
The direct supply that (2) step arranges in described iron anode pretreatment unit contains two reometers, and two reometers connect respectively two anodes.
The distance that (2) step installs between electrode in described iron anode pretreatment unit is 0.5～10cm, and design spacing between electrodes is little, makes the resistance that forms between electrode little, is conducive to reduce power consumption.
The step (2) described control current ratio by iron anode and anode I is 1 ︰ 1～2 ︰ 1.
Step (3) described granule filter material is diameter 0.5～5mm quartz sand or coal particle.
Step is described palladium catalyst aluminum oxide or the activated carbon particle of palladium of having selected commercially available load (4).
Step is (6) described carries out energy optimization according to repairing effect, and concrete control method is:
1. feed water flow speed is regulated, in treated water outlet, Pollutant levels, lower than the standard of setting, improve water-in water flow velocity, otherwise reduce water-in water flow velocity, make pollutent have enough residence time in palladium catalyzed reaction unit, guarantee treated water outlet place water quality reaching standard;
2. total current is regulated, if groundwater intake place's reduced sulfur and calcium ions and magnesium ions concentration are higher than the standard of setting, improve total current, otherwise reduce total current, to guarantee that palladium catalyst does not lose activity and reduces power consumption.
Method of the present invention can overcome and avoid the hydrogen transportation and preservation difficulty, the palladium catalyst that in traditional palladium catalytic hydrogenating reduction technological method, need in actual groundwater environment, to be easily reduced the murders by poisoning such as state sulphur and calcium magnesium hardness and the shortcomings such as inactivation.Method of the present invention can provide the pollutent reduction effect of continuous and effective in underground water repairing environment.
Compared with the prior art the underground water restorative procedure of iron anode coupling palladium shortening of the present invention has the following advantages:
1. method of the present invention is compared with traditional palladium catalytic hydrogenating reduction technology, the method of supplying of hydrogen is added to change to by negative electrode in-situ electrolysis by external source and produce, reduce transportation and the storage difficulty of a large amount of external source hydrogen, and saved the equipment that hydrogen dissolving mixes.
2. method of the present invention can be removed the underground water composition that affects palladium catalytic reduction activity by in-situ chemical reaction and throwing out, extends the work-ing life of palladium catalyst, improves catalytic efficiency.
3. method of the present invention is distributed by the electric current of regulation and control total current and two anodes, by anode I, shared the electric current of iron anode, reduce the consumption of iron anode, and the hydrogen ion that anode I produces can neutralize the hydroxide ion that part negative electrode produces, guarantee that water outlet pH=6～9 are neutral water, having avoided traditional method water outlet is the potential risk that peracid or mistake buck cause.
4. the oxygen that method inert anode I of the present invention produces can suppress the growth procreation of sulphur reducing bacteria, thereby reduces negative divalent sulfur content in underground water, reduces the possibility of palladium catalyst inactivation.
5. the inventive method has good, the easy to operate and environmental friendliness for the treatment of effect, and in method, whole treatment unit is safeguarded simple.
Accompanying drawing explanation
Fig. 1 is the inventive method is carried out simulated experiment device schematic diagram in laboratory.
Fig. 2 is application trieline concentration C and underground water influent concentration C in treated water outlet water during the inventive method
0the time dependent figure of ratio.
Fig. 3 is the apparatus structure of the inventive method use and the schematic flow sheet that carries out underground water reparation.
In above-mentioned figure: 1-iron anode pretreatment unit; 2-sand filtration unit; 3-palladium catalyzed reaction unit; 10-water pump; 11-groundwater intake; 12-water receptacle; 13-anode I; 14-negative electrode; 15-iron anode; 16-first step water outlet; 17-direct supply; 18-reometer II; 19-reometer I; 21-sand filtration container; 22-granule filter material; 23-porous barrier; 24-second stage water outlet; 31-catalyticreactor; 32-palladium catalyst; 33-treated water outlet.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1: the present invention first provides a kind of underground water restorative procedure at laboratory simulation iron anode coupling palladium shortening, the present embodiment mainly contains trieline pollutent (trichloroethylene in the simulated groundwater of chamber by experiment, abbreviation TCE) reparation, as follows operation:
Step (1), is first prepared one and is enclosed within the device that the underground water reparation of iron anode coupling palladium shortening is carried out in laboratory, and this apparatus structure as shown in Figure 1, comprises iron anode pretreatment unit 1, sand filtration unit 2 and palladium catalyzed reaction unit 3; Three unit are indispensable, and three unit are linked in sequence.
Step (2), iron anode pretreatment unit 1 is installed, iron anode pretreatment unit 1 comprises a water receptacle 12, water receptacle internal diameter 25mm, high 200mm, be provided with groundwater intake 11 and first step water outlet 16, anodic-cathodic is installed in water receptacle, along Groundwater flow path direction, anode I 13, negative electrode 14, iron anode 15 is installed successively; In groundwater intake, one side cross section is first installed anode I 13, its Anodic I 13, the equal choice for use holey titanium coated electrode of negative electrode 14, and iron anode 15 is selected to be equipped with very lacunary iron plate electrode, and three electrodes are all diameter 25mm, thickness 17mm; Adopt netted and plate electrode porous, be conducive to water flow and improve current efficiency; Three interelectrode distances are 5mm.Outer setting direct supply 17 and water pump 10 at water receptacle; Direct supply 17 provides electric current to three electrodes for constant voltage dc source.Direct supply is provided with two reometers and two output terminals, and reometer I 19 is connected with anode I 13, and reometer II 18 is connected with iron anode 15, the positive pole of two output terminals respectively with two anodic bondings, the negative pole of two output terminals is all connected with negative electrode.Adopt water pump 10 that underground water is pumped in water receptacle 12 by groundwater intake 11.
Step (3), sand filtration unit 2 is installed, because experimental installation is miniature device, in experimental installation, sand filtration unit 2 is arranged on above iron anode pretreatment unit 1, and will between the water receptacle of iron anode pretreatment unit 12 and the sand filtration container 21 of sand filtration unit, adopt lucite spacer to separate, and dummy plate is become to porous barrier 23, the aperture in porous barrier 23 is as the first step water outlet 16 of iron anode pretreatment unit 1.The high 70mm of sand filtration container 21 of sand filtration unit 2, in sand filtration container, filler particles filtrate 22 is diameter 0.5～1mm quartz sand particle filtrate, the iron throw out that quartz sand particle filtrate produces for filtering iron anode pretreatment unit 1 and the particulate matter of underground water.
Step (4), palladium catalyzed reaction unit 3 is installed, described palladium catalyzed reaction unit 3 comprises a catalyticreactor 31, catalyticreactor is diameter 7mm, the thin right cylinder of high 150mm, palladium catalyst 32 is selected the Pd/Al of quality 2g
2o
3particle, Pd mass ratio is 0.5%, and the granulated glass sphere that mixes diameter 3mm is filled in reactor, makes porosity in 0.38 left and right, catalyticreactor 31 tops are provided with treated water outlet 33.
(5), the water-in of the 24 use flexible pipes of the second stage water outlet on sand filtration unit 2 and palladium catalyzed reaction unit 3 is connected, a whole set of experimental installation has installed step.Carrying out before underground water is repaired preparing contaminated underground water for simulating: prepared 1L containing 10mg/L trieline, and containing 5mmol/L NaHCO
3, 3mmol/L Na
2sO
4, in order to simulate Polluted Groundwater, initial dissolution oxygen concn≤0.3mg/L.By peristaltic pump by simulated groundwater injected water container 12, before energising first with 2 times device void volumes simulate formation water flushing devices.
While carrying out simulated groundwater reparation, controlling flow velocity enters in the water receptacle 12 of iron anode pretreatment unit 1 at 1.5mL/min, connect direct supply 17 simultaneously, regulate by the reometer of two output terminals, controlling iron anode 15 is that 10mA/10mA and 13.3mA/6.7mA test with anode I 13 current ratios, and the underground water of pollution flows through anode I 13, negative electrode 14, iron anode 15 successively.Underground water, by anode I, produces hydrogen ion and oxygen in anode I, has small portion reduced sulfur to be oxidized in anode I in underground water; Underground water enters negative electrode and iron anode region subsequently, at negative electrode 14, produces hydroxide ion and hydrogen; The hydrogen constantly producing at this region negative electrode makes the saturated dissolved hydrogen of underground water, at iron anode 15, produce ferrous ion, the hydroxide radical that ferrous ion produces with negative electrode is rapidly combined and is generated ferrous hydroxide, and ferrous hydroxide generates ironic hydroxide throw out by the oxygen reduction producing from anode I 13; Ferrous ion is in conjunction with ferric iron throw out, for removing reduced sulfur, calcium magnesium hardness and the part microorganism of underground water, for the reaction of follow-up palladium catalyst provides good environment.
Simulated groundwater enters sand filtration unit 2 after iron anode pretreatment unit 1, goes back the quartz sand particle filtrate 22 that remainder iron throw out filled in sand filtration container and hold back in underground water; Make to have removed in underground water the material poisonous to palladium catalyst, and in underground water, dissolved in hydrogen.When underground water flows into palladium catalyzed reaction unit 3 again, solubilised state hydrogen is removed the TCE pollutent reduction in underground water efficiently under palladium katalysis, and TCE is reduced into the non-toxic substances such as ethane and ethylene.
Step (6), monitoring processes organic concentration height in after purification water out 33, according to underground water repairing effect, carry out energy optimization, the present embodiment is mainly by the variation of different time points water outlet TCE concentration in simulated experiment detection reaction process, and compare i.e. C/C with the TCE starting point concentration in configured underground water
0, acquired results is referring to Fig. 2, and when iron anode 15 and anode I 13 current ratios are 1 ︰ 1 and 2:1, water outlet TCE concentration is reduced to below 20% as seen from Figure 2, and the clearance of TCE can reach more than 80%, and keeps stable.
Embodiment 2: the invention provides a kind of iron anode coupling palladium shortening to polluted underground water restorative procedure, the present embodiment for to build a covering device with inert materials such as UPVC near Polluted Groundwater place, for the reparation to nitro-compound polluted underground water, described apparatus structure and reparation flow process are as shown in Figure 3, adopt iron anode coupling palladium shortening to polluted underground water restorative procedure, its concrete operations at least comprise the steps:
Step (1), a constructed covering device, comprise iron anode pretreatment unit 1, sand filtration unit 2 and palladium catalyzed reaction unit 3, water receptacle 12 in three unit, sand filtration container 21 and catalyticreactor 31 are cylindric, internal diameter 6cm, height 70cm, be equipped with entery and delivery port, by pipeline, be linked in sequence.
Step (2), iron anode pretreatment unit 1 is installed, wherein water receptacle inside is provided with three electrodes, parallel installation anode I 13 successively from top to bottom vertically, negative electrode 14, iron anode 15, anode I 13 is arranged on apart from water receptacle 12 10cm places, bottom, and three electrode diameters are identical with sand filtration container 21 internal diameters, and three electrode spacing is 2cm.At water receptacle 12 outer setting direct supplys 17, the 11 front installation water pumps 10 in groundwater intake, first step water outlet 16 is established on water receptacle 12 tops, by pipeline, is connected with sand filtration unit 2.
Step (3), sand filtration unit 2 is installed, the inert particle filtrate 22 of sand filtration container 21 interior fillings is selected 1～5mm coal grain, the second stage water outlet 24 of sand filtration unit 2 is connected with the reactor water-in of palladium catalyzed reaction unit 3 by pipeline.
Step (4), palladium catalyzed reaction unit 3 is installed, catalyticreactor 31 tops arrange treated water outlet 33, the interior filling palladium catalyst 32 of catalyticreactor 31, palladium catalyst 32 the has been selected commercially available 1Kg diameter 1.5～5.0mm load alumina particle of palladium, palladium metal mass ratio is 0.5%, and the granulated glass sphere that mixes about diameter 3mm is filled in reactor, make porosity in 0.48 left and right.
Step (5), carry out underground water reparation after installing complete assembly, its process is: by water pump 10, with 6L/h flow, extract the underground water polluting, be introduced into iron anode pretreatment unit 1, by direct supply 17 output total current 400mA, it is 1 ︰ 1 that two output terminals distribute anode I 13 and iron anode 15 current ratios, underground water passes through anode I 13, negative electrode 14 and iron anode 15 successively again by sand filtration unit 2, finally enters palladium catalyzed reaction unit 3 and reacts removal pollutent.
Step (6), detect the concentration of underground water pollutant, flooding velocity is regulated, if Pollutant levels are too much lower than standard in the water outlet of treated water outlet 33, can suitably improve flooding velocity.Otherwise can reduce flooding velocity, make pollutent have enough residence time in palladium catalytic reduction unit, guarantee treated water outlet 33 to go out water concentration up to standard.
Embodiment 3: the invention provides a kind of iron anode coupling palladium shortening to polluted underground water restorative procedure, present method for to construct a covering device with materials such as UPVC near Polluted Groundwater field, for the reparation to chloro organic contamination underground water, device outfit and operating process thereof are with embodiment 2, that different is water receptacle 12 internal diameter 15cm in iron anode pretreatment unit, height 200cm, interelectrode distance is 10cm; The sand filtration container 21 internal diameter 10cm of sand filtration unit, height 100cm, palladium catalytic hydrogenating reduction unit internal diameter 15cm, height 300cm, fills palladium catalyst 25Kg, and in simultaneous reactions device, weighting material porosity is 0.5; The water speed control that treating processes underground water flows into is built in 7.5L/min, and direct supply 17 is exported total current 600mA, and it is 2 ︰ 1 that two output terminals distribute iron anode 15 and anode I 13 current ratios.Equally according to the height of reduced sulfur and calcium ions and magnesium ions concentration in underground water before processing, can regulate total current, if water inlet reduced sulfur and calcium ions and magnesium ions concentration is higher improves total current, on the contrary can reduce total current, to guarantee that palladium catalyst does not lose activity and reduces power consumption.
Method of the present invention is according to the characteristic of underground water, parameter request for palladium catalytic hydrogenating reduction technology, electrochemistry is combined with palladium catalytic hydrogenating reduction technology, overcome transportation and the storage difficult problem of a large amount of external source hydrogen of traditional palladium catalytic hydrogenating reduction Technology Need, and improved the chemical reduction efficiency of pollutent.Present method has that processing efficiency is high, the treatment time is short, flexible operation, device safeguard simple, level of automation is high and the feature such as environmental friendliness, is specially adapted to the reparation of the vattability species contaminated site underground water such as chlorinatedorganic, nitro-compound.
Claims (8)
1. a underground water restorative procedure for iron anode coupling palladium shortening, is characterized in that: operation as follows:
Step (1), prepare a set of underground water prosthetic device that carries out iron anode coupling palladium shortening, comprise iron anode pretreatment unit, sand filtration unit and palladium catalyzed reaction unit, three unit connect by pipeline;
Step (2), iron anode pretreatment unit is installed, iron anode pretreatment unit comprises a water receptacle, water receptacle is provided with groundwater intake and first step water outlet, and anodic-cathodic is installed in water receptacle, along Groundwater flow path direction, anode I, negative electrode, iron anode is installed successively; In water receptacle, groundwater intake one side cross section is first installed anode I, and anode I selects titanium coating class inactive, conductive material to make, and negative electrode selects stainless steel plate or titanium coating electro-conductive material to make; Iron anode selects common iron material to make; Three electrodes all adopt plate electrode netted or that be evenly with holes, are conducive to water flow and improve current efficiency; At outer setting water pump and the direct supply of water receptacle, adopt water pump that underground water is pumped in water receptacle, by the direct supply of peripheral hardware, to three electrodes of yin, yang, provide electric current, and control by the current ratio of iron anode and anode I;
Step (3), sand filtration unit is installed, described sand filtration unit is connected between iron anode pretreatment unit and palladium catalyzed reaction unit, sand filtration unit comprises a sand filtration container, be provided with the sand filtration container water-in and the second stage water outlet that are connected with palladium catalyzed reaction unit with iron anode pretreatment unit, filler particles filtrate in sand filtration container, the iron throw out that sand filtration container produces for filtering iron anode pretreatment unit and the particulate matter of underground water;
Step (4), palladium catalyzed reaction unit is installed, described palladium catalyzed reaction unit comprises a catalyticreactor, the reactor water-in being connected with second stage water outlet is established in bottom, top is provided with treated water outlet, select the solid palladium granules of catalyst that diameter 1.5～5.0mm and palladium mass content are 0.5%～5%, and the granulated glass sphere that mixes diameter 2～4mm is filled in reactor, make to fill rear porosity 0.35～0.5;
Step (5), connect the pipeline of three unit; Start mounted device and carry out underground water reparation: by water pump, extract polluted underground water, switch on power simultaneously; The underground water polluting is introduced into iron anode pretreatment unit, flows through successively anode I, negative electrode, iron anode, then by sand filtration unit, finally enters palladium catalyzed reaction unit and react removal pollutent;
The underground water polluting is by anode I, and anode I, for generation of hydrogen ion and oxygen, has small portion reduced sulfur in the oxidation of anode I in the underground water of pollution, and underground water enters negative electrode and iron anode region subsequently, and negative electrode is for generation of hydroxide ion and hydrogen; The hydrogen constantly producing at this region negative electrode makes the saturated dissolved hydrogen of underground water, iron anode is for generation of ferrous ion, the hydroxide radical that ferrous ion produces with negative electrode is rapidly combined and is generated ferrous hydroxide, and ferrous hydroxide generates ironic hydroxide throw out by the oxygen reduction producing from anode I; Ironic hydroxide throw out is for reduced sulfur, calcium magnesium hardness and the part microorganism of removing underground water, for the reaction of follow-up palladium catalyst provides good environment;
The underground water polluting is flowed out and is entered sand filtration unit by first step water outlet after iron anode pretreatment unit, and underground water now also remainder iron throw out is held back by the granule filter material of filling in sand filtration container; Remove material poisonous to palladium catalyst in underground water, and in underground water, dissolved in hydrogen;
Behind sand filtration unit, when underground water flows into palladium catalyzed reaction unit from second stage water outlet, solubilised state hydrogen is removed underground water pollutant reduction efficiently under palladium katalysis, and the water after processing flows out from treated water outlet;
Step (6), monitoring processes organic concentration height in after purification water out, according to underground water repairing effect, carries out energy optimization, adopts feed water flow speed is regulated, or total current is regulated to optimization energy consumption.
2. the underground water restorative procedure of iron anode according to claim 1 coupling palladium shortening, it is characterized in that: iron anode pretreatment unit, sand filtration unit and palladium catalyzed reaction unit in the step device that (1) described underground water is repaired, three unit are indispensable, and are linked in sequence.
3. the underground water restorative procedure of iron anode according to claim 1 coupling palladium shortening, is characterized in that: the direct supply that (2) step arranges in described iron anode pretreatment unit contains two reometers, and two reometers connect respectively two anodes.
4. the underground water restorative procedure of iron anode according to claim 1 coupling palladium shortening, it is characterized in that: the distance that (2) step installs between electrode in described iron anode pretreatment unit is 0.5～10cm, design spacing between electrodes is little, make the resistance that forms between electrode little, be conducive to reduce power consumption.
5. the underground water restorative procedure of iron anode according to claim 1 coupling palladium shortening, is characterized in that: the step (2) described control current ratio by iron anode and anode I is 1 ︰ 1～2 ︰ 1.
6. the underground water restorative procedure of iron anode according to claim 1 coupling palladium shortening, is characterized in that: step (3) described granule filter material is diameter 0.5～5mm quartz sand or coal particle.
7. the underground water restorative procedure of iron anode according to claim 1 coupling palladium shortening, is characterized in that: step is described palladium catalyst aluminum oxide or the activated carbon particle of palladium of having selected commercially available load (4).
8. the underground water restorative procedure of iron anode according to claim 1 coupling palladium shortening, is characterized in that: step is (6) described carries out energy optimization according to repairing effect, and concrete control method is:
1. feed water flow speed is regulated, in treated water outlet, Pollutant levels, lower than the standard of setting, improve water-in water flow velocity, otherwise reduce water-in water flow velocity, make pollutent have enough residence time in palladium catalyzed reaction unit, guarantee treated water outlet place water quality reaching standard;
2. total current is regulated, if groundwater intake place's reduced sulfur and calcium ions and magnesium ions concentration are higher than the standard of setting, improve total current, otherwise reduce total current, to guarantee that palladium catalyst does not lose activity and reduces power consumption.
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| CN110357348A (en) * | 2019-06-27 | 2019-10-22 | 中国地质大学（武汉） | A kind of chlorohydrocarbon polluted underground water electrochemical in-situ circulation well restorative procedure |
| CN111718039A (en) * | 2020-05-13 | 2020-09-29 | 中国地质大学（武汉） | Method and device for treating multiple kinds of chlorohydrocarbon composite pollution in underground water |
| CN113149150A (en) * | 2021-04-25 | 2021-07-23 | 中国地质大学（武汉） | Activated carbon cathode electro-Fenton system and method for removing underground water halogenated hydrocarbons by using same |
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| CN110357348A (en) * | 2019-06-27 | 2019-10-22 | 中国地质大学（武汉） | A kind of chlorohydrocarbon polluted underground water electrochemical in-situ circulation well restorative procedure |
| CN110357348B (en) * | 2019-06-27 | 2021-12-28 | 中国地质大学（武汉） | In-situ electrochemical circulation well repairing method for chlorohydrocarbon polluted underground water |
| CN111718039A (en) * | 2020-05-13 | 2020-09-29 | 中国地质大学（武汉） | Method and device for treating multiple kinds of chlorohydrocarbon composite pollution in underground water |
| CN113149150A (en) * | 2021-04-25 | 2021-07-23 | 中国地质大学（武汉） | Activated carbon cathode electro-Fenton system and method for removing underground water halogenated hydrocarbons by using same |
| CN116395804A (en) * | 2023-06-08 | 2023-07-07 | 内蒙古工业大学 | Filling anode electrochemical sewage treatment device with catalysis function |
| CN116395804B (en) * | 2023-06-08 | 2023-08-08 | 内蒙古工业大学 | Filling anode electrochemical sewage treatment device with catalysis function |
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