CN104016531B - 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.Be specially the groundwater remediation method of a kind of iron anode coupling palladium chtalyst hydrogenation, be specially adapted to the reparation of the vattability such as chlorinatedorganic, nitro-compound species contaminated site underground water.
Background technology
Current China groundwater pollution situation is very severe, and the initial investigation results according to " national pollution prevention plan (2010 – the year two thousand twenty) " shows, and China 90% urban groundwater suffers the pollution of toxic pollutant in various degree.
Traditional groundwater remediation technology 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 chtalyst hydrogenating reduction technology is risen in developed country in the nineties in last century, repairs rapidly and efficiently, can 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 chtalyst hydrogenating reduction uses is supplied by compression hydrogen, needs to increase hydrogen and dissolves mixing equipment, and the inflammable and explosive characteristic of hydrogen, add 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 chtalyst is expensive, in order to extend its work-ing life, way common at present regularly uses strong oxidizer to regenerate palladium catalyst, but regenerative process inevitably causes the loss of palladium content, and can not activity recovery completely, regenerative process also increases difficulty and the cost of system cloud gray model management.These problems make the actual site remediation application of palladium chtalyst reduction technique also fewer.
Summary of the invention
The present invention seeks to the deficiency existed to solve prior art, and a kind of original position supply and the catalyst deactivation probiems that effectively can solve hydrogen in underground water palladium chtalyst hydrogenating reduction process are provided, and easy to operate, safeguard that the good and eco-friendly iron anode of simple, treatment effect is coupled palladium chtalyst hydrogenation groundwater remediation method.
For achieving the above object, the technical scheme that the present invention takes is: provide the groundwater remediation method that a kind of iron anode is coupled palladium chtalyst hydrogenation, operates as follows:
Step (1), prepare a set of groundwater remediation device carrying out iron anode coupling palladium chtalyst hydrogenation, comprise iron anode pretreatment unit, sand filtration unit and palladium-catalyzed reaction unit, three unit are connected 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, is provided with anodic-cathodic in water receptacle, installs anode I, negative electrode, iron anode successively along Groundwater flow path direction; In water receptacle, side, groundwater intake cross section first installs 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 general ferrite material to make; Three electrodes all adopt plate electrode that is 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 to pump in water receptacle by underground water, provide electric current by the direct supply of peripheral hardware to yin, yang three electrodes, and control the current ratio by 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, one end that sand filtration container is connected with iron anode pretreatment unit is provided with water-in, one end that sand filtration container is connected with palladium-catalyzed reaction unit is provided with second stage water outlet, filler particles filtrate in sand filtration container, sand filtration container be used for filtering iron anode pretreatment unit produce iron throw out and underground water in particulate matter;
Step (4), palladium-catalyzed reaction unit is installed, described palladium-catalyzed reaction unit comprises a catalyticreactor, the reactor water-in be connected with second stage water outlet is established in bottom, top is provided with treated water outlet, select diameter 1.5 ~ 5.0mm and palladium mass content be 0.5% ~ 5% solid palladium granules of catalyst, and the granulated glass sphere mixing diameter 2 ~ 4mm is filled in reactor, after making filling, porosity is 0.35 ~ 0.5;
Step (5), connect the pipeline of three unit; Start mounted device and carry out groundwater remediation: extract polluted underground water by water pump, switch on power simultaneously; The underground water polluted is introduced into iron anode pretreatment unit, flows through anode I, negative electrode, iron anode successively, then by sand filtration unit, finally enters palladium-catalyzed reaction unit and carry out reaction removal pollutent;
The underground water polluted is by anode I, and anode I is for generation of hydrogen ion and oxygen, and have small portion reduced sulfur in the underground water of pollution in anode I oxidation, underground water enters negative electrode and iron anode region subsequently, and negative electrode is for generation of hydroxide ion and hydrogen; The hydrogen constantly produced at this region negative electrode makes the saturated dissolved hydrogen of underground water, iron anode is for generation of ferrous ion, ferrous ion is combined with the hydroxide radical that negative electrode produces rapidly and generates ferrous hydroxide, and the oxygen reduction produced from anode I is generated ironic hydroxide throw out by ferrous hydroxide; Ironic hydroxide throw out is for removing reduced sulfur in underground water, calcium magnesium hardness and part microorganism, and the reaction for follow-up palladium catalyst provides good environment;
The underground water polluted is flowed out by first step water outlet and enters sand filtration unit after iron anode pretreatment unit, and underground water now also remainder iron throw out is retained by the granule filter material of filling in sand filtration container; Eliminate material poisonous to palladium catalyst in underground water, and in underground water, dissolve in hydrogen;
After sand filtration unit, when underground water flows into palladium-catalyzed reaction unit from second stage water outlet, water pollutant reduction in underground is removed efficiently by solubilised state hydrogen under palladium chtalyst effect, and the water after process flows out from treated water outlet;
Step (6), organic concentration level in monitoring process after purification water out, carry out energy optimization according to underground water repairing effect, adopt and feed water flow speed is regulated, or adjustments optimization energy consumption is carried out to total current.
In the present invention the groundwater remediation that step is (1) described device in iron anode pretreatment unit, sand filtration unit and palladium-catalyzed reaction unit, three unit are indispensable, and are linked in sequence.
The direct supply arranged in the iron anode pretreatment unit that step is (2) described contains two reometers, and two reometers connect two anodes respectively.
The distance of installing between electrode in the iron anode pretreatment unit that step is (2) described is 0.5 ~ 10cm, and design spacing between electrodes is little, makes the resistance that formed between electrode little, is conducive to reducing power consumption.
The (2) described control of step is 1 ︰ 1 ~ 2 ︰ 1 by the current ratio of iron anode and anode I.
The (3) described granule filter material of step is diameter 0.5 ~ 5mm quartz sand or coal particle.
The (4) described palladium catalyst of step selects aluminum oxide or the activated carbon particle of commercially available load palladium.
Step is (6) described carries out energy optimization according to repairing effect, and concrete control method is:
1. feed water flow speed is regulated, when Pollutant levels in treated water outlet are lower than the standard of setting, then improve water-in water flow velocity, otherwise then reduce water-in water flow velocity, make pollutent have enough residence time at palladium-catalyzed reaction unit, ensure treated water outlet place water quality reaching standard;
2. total current is regulated, if groundwater intake place reduced sulfur and calcium ions and magnesium ions concentration are higher than the standard of setting, then improve total current, otherwise then reduce total current, to ensure that palladium catalyst does not lose activity and reduces power consumption.
Method of the present invention can overcome and avoid the hydrogen needed in traditional palladium chtalyst hydrogenating reduction technological method to transport and preservation is difficult, palladium catalyst is easily reduced the murder by poisoning such as state sulphur and calcium magnesium hardness in actual groundwater environment and the shortcomings such as inactivation.Method of the present invention can provide the pollutent reduction effect of continuous and effective in groundwater remediation environment.
Compared with the prior art the groundwater remediation method of iron anode coupling palladium chtalyst hydrogenation of the present invention has the following advantages:
1. method of the present invention is compared with traditional palladium chtalyst hydrogenating reduction technology, the method of supplying of hydrogen is added to change to by external source and is produced by negative electrode in-situ electrolysis, decrease the transport of a large amount of external source hydrogen and store difficulty, and eliminating the equipment that hydrogen dissolves mixing.
2. method of the present invention can remove by in-situ chemical reaction and throwing out the underground water composition affecting palladium chtalyst reducing activity, 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, the electric current of iron anode has been shared by anode I, reduce the consumption of iron anode, and the hydrogen ion that anode I produces can neutralize the hydroxide ion that part negative electrode produces, ensure that water outlet pH=6 ~ 9 are neutral water, avoiding 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 of sulphur reducing bacteria to be multiplied, thus 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 carries out simulated experiment device schematic diagram in laboratory.
Fig. 2 is trieline concentration C and underground water influent concentration C in treated water outlet water during application the inventive method
0the time dependent figure of ratio.
Fig. 3 is the apparatus structure that the inventive method uses and the schematic flow sheet carrying out groundwater remediation.
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 groundwater remediation method at laboratory simulation iron anode coupling palladium chtalyst hydrogenation, the present embodiment is mainly through containing trieline pollutent (trichloroethylene in laboratory simulation underground water, be called for short TCE) reparation, as follows operate:
Step (1), first prepares one and is enclosed within the device that the groundwater remediation of iron anode coupling palladium chtalyst hydrogenation 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, in water receptacle, anodic-cathodic is installed, along Groundwater flow path direction, anode I 13, negative electrode 14, iron anode 15 is installed successively; In side, groundwater intake, cross section first installs anode I 13, and its Anodic I 13, negative electrode 14 be choice for use holey titanium coating electrode all, 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 that is porous, be conducive to water flow and improve current efficiency; Three interelectrode distances are 5mm.At outer setting direct supply 17 and the water pump 10 of water receptacle; Direct supply 17 provides electric current to three electrodes for constant voltage dc source.Direct supply is provided with two pieces of 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, and the positive pole of two output terminals is connected with two anodes respectively, and the negative pole of two output terminals is all connected with negative electrode.Water pump 10 is adopted to be pumped in water receptacle 12 by groundwater intake 11 by underground water.
Step (3), sand filtration unit 2 is installed, due to the device that experimental installation is miniature, in experimental installation, sand filtration unit 2 is arranged on above iron anode pretreatment unit 1, and adopt lucite spacer to separate by between the water receptacle 12 of iron anode pretreatment unit and the sand filtration container 21 of sand filtration unit, and dummy plate is become 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, quartz sand particle filtrate be used for filtering iron anode pretreatment unit 1 produce iron throw out and underground water in particulate matter.
Step (4), palladium-catalyzed reaction unit 3 is installed, described palladium-catalyzed reaction unit 3 comprises a catalyticreactor 31, and catalyticreactor is diameter 7mm, and the thin right cylinder of high 150mm, the Pd/Al of quality 2g selected by palladium catalyst 32
2o
3particle, Pd mass ratio is 0.5%, and the granulated glass sphere mixing diameter 3mm is filled in reactor, makes porosity about 0.38, and catalyticreactor 31 top is provided with treated water outlet 33.
(5), by the water-in of the second stage water outlet 24 on sand filtration unit 2 with flexible pipe and palladium-catalyzed reaction unit 3 step connects, and a whole set of experimental installation has installed.Be the contaminated underground water of simulation preparation before carrying out groundwater remediation: 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, simulated groundwater is injected water receptacle 12, before energising, first use the simulate formation water flushing device of 2 times of device void volumes.
When 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 the reometer by two output terminals, controlling iron anode 15 with anode I 13 current ratio is that 10mA/10mA and 13.3mA/6.7mA tests, 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 at anode I, has small portion reduced sulfur in anode I oxidation in underground water; Underground water enters negative electrode and iron anode region subsequently, produces hydroxide ion and hydrogen at negative electrode 14; The hydrogen constantly produced at this region negative electrode makes the saturated dissolved hydrogen of underground water, ferrous ion is produced at iron anode 15, ferrous ion is combined with the hydroxide radical that negative electrode produces rapidly and generates ferrous hydroxide, and the oxygen reduction produced from anode I 13 is generated ironic hydroxide throw out by ferrous hydroxide; Ferrous ion is in conjunction with ferric iron throw out, and for removing reduced sulfur in underground water, calcium magnesium hardness and part microorganism, the reaction for follow-up palladium catalyst provides good environment.
Simulated groundwater enters sand filtration unit 2 after iron anode pretreatment unit 1, goes back remainder iron throw out and retained by the quartz sand particle filtrate 22 of filling in sand filtration container in underground water; Make in underground water, to eliminate the material poisonous to palladium catalyst, and in underground water, dissolved in hydrogen.When underground water flows into palladium-catalyzed reaction unit 3 again, the TCE pollutent reduction in underground water is removed efficiently by solubilised state hydrogen under palladium chtalyst effect, and namely TCE is reduced into the non-toxic substances such as ethane and ethylene.
Step (6), organic concentration level in monitoring process after purification water out 33, energy optimization is carried out according to underground water repairing effect, the present embodiment is mainly through the change of different time points water outlet TCE concentration in simulated experiment detection reaction process, and compare with the TCE starting point concentration in configured underground water, i.e. C/C
0, acquired results is see Fig. 2, and when iron anode 15 is 1 ︰ 1 and 2:1 with anode I 13 current ratio, water outlet TCE concentration is reduced to less than 20% as seen from Figure 2, and namely the clearance of TCE can reach more than 80%, and keeps stable.
Embodiment 2: the invention provides a kind of iron anode coupling palladium chtalyst hydrogenation to polluted underground water restorative procedure, the present embodiment is build set of 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 chtalyst hydrogenation to polluted underground water restorative procedure, its concrete operations at least comprise the steps:
Step (1), constructed set of 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, be linked in sequence by pipeline.
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 10cm place bottom water receptacle 12, and three electrode diameters are identical with sand filtration container 21 internal diameter, and three electrode spacing is 2cm.At water receptacle 12 outer setting direct supply 17, before groundwater intake 11, install water pump 10, first step water outlet 16 is established on water receptacle 12 top, is connected with sand filtration unit 2 by pipeline.
Step (3), sand filtration unit 2 is installed, 1 ~ 5mm coal grain selected by the inert particle filtrate 22 of filling in sand filtration container 21, and 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 top arranges treated water outlet 33, palladium catalyst 32 is filled in catalyticreactor 31, commercially available 1Kg diameter 1.5 ~ 5.0mm load alumina particle of palladium selected by palladium catalyst 32, palladium metal mass ratio is 0.5%, and the granulated glass sphere mixing diameter about 3mm is filled in reactor, make porosity about 0.48.
Step (5), install complete assembly after carry out groundwater remediation, its process is: extracted the underground water polluted with 6L/h flow by water pump 10, be introduced into iron anode pretreatment unit 1, total current 400mA is exported by direct supply 17, two output terminal distribution anodes I 13 and iron anode 15 current ratio are 1 ︰ 1, underground water passes through sand filtration unit 2 again by anode I 13, negative electrode 14 and iron anode 15 successively, finally enters palladium-catalyzed reaction unit 3 and carries out reaction 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, then suitably can improve flooding velocity.Otherwise then can reduce flooding velocity, make pollutent have enough residence time at palladium chtalyst reduction unit, ensure that the aqueous concentration of treated water outlet 33 is up to standard.
Embodiment 3: the invention provides a kind of iron anode coupling palladium chtalyst hydrogenation to polluted underground water restorative procedure, present method for construct set of 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, unlike 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 chtalyst hydrogenating reduction unit internal diameter 15cm, height 300cm, fill palladium catalyst 25Kg, 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 exports total current 600mA, and two output terminal distribution iron anodes 15 and anode I 13 current ratio are 2 ︰ 1.Equally according to the height of reduced sulfur and calcium ions and magnesium ions concentration in underground water before process, can regulate total current, if water inlet reduced sulfur and calcium ions and magnesium ions concentration higher, improve total current, otherwise then can reduce total current, to ensure that palladium catalyst does not lose activity and reduces power consumption.
Method of the present invention is according to the characteristic of underground water, for the parameter request of palladium chtalyst hydrogenating reduction technology, electrochemistry is combined with palladium chtalyst hydrogenating reduction technology, overcome traditional palladium chtalyst hydrogenating reduction technology need the transport of a large amount of external source hydrogen and store a difficult problem, and improve 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 such as chlorinatedorganic, nitro-compound species contaminated site underground water.
Claims (8)
1. a groundwater remediation method for iron anode coupling palladium chtalyst hydrogenation, is characterized in that: operate as follows:
Step (1), prepare a set of groundwater remediation device carrying out iron anode coupling palladium chtalyst hydrogenation, comprise iron anode pretreatment unit, sand filtration unit and palladium-catalyzed reaction unit, three unit are connected 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, is provided with anodic-cathodic in water receptacle, installs anode I, negative electrode, iron anode successively along Groundwater flow path direction; In water receptacle, side, groundwater intake cross section first installs 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 general ferrite material to make; Three electrodes all adopt plate electrode that is 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 to pump in water receptacle by underground water, provide electric current by the direct supply of peripheral hardware to yin, yang three electrodes, and control the current ratio by 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, one end that sand filtration container is connected with iron anode pretreatment unit is provided with water-in, one end that sand filtration container is connected with palladium-catalyzed reaction unit is provided with second stage water outlet, filler particles filtrate in sand filtration container, sand filtration container be used for filtering iron anode pretreatment unit produce iron throw out and underground water in particulate matter;
Step (4), palladium-catalyzed reaction unit is installed, described palladium-catalyzed reaction unit comprises a catalyticreactor, the reactor water-in be connected with second stage water outlet is established in bottom, top is provided with treated water outlet, select diameter 1.5 ~ 5.0mm and palladium mass content be 0.5% ~ 5% solid palladium granules of catalyst, and the granulated glass sphere mixing diameter 2 ~ 4mm is filled in reactor, after making filling, porosity is 0.35 ~ 0.5;
Step (5), connect the pipeline of three unit; Start mounted device and carry out groundwater remediation: extract polluted underground water by water pump, switch on power simultaneously; The underground water polluted is introduced into iron anode pretreatment unit, flows through anode I, negative electrode, iron anode successively, then by sand filtration unit, finally enters palladium-catalyzed reaction unit and carry out reaction removal pollutent;
The underground water polluted is by anode I, and anode I is for generation of hydrogen ion and oxygen, and have small portion reduced sulfur in the underground water of pollution in anode I oxidation, underground water enters negative electrode and iron anode region subsequently, and negative electrode is for generation of hydroxide ion and hydrogen; The hydrogen constantly produced at this region negative electrode makes the saturated dissolved hydrogen of underground water, iron anode is for generation of ferrous ion, ferrous ion is combined with the hydroxide radical that negative electrode produces rapidly and generates ferrous hydroxide, and the oxygen reduction produced from anode I is generated ironic hydroxide throw out by ferrous hydroxide; Ironic hydroxide throw out is for removing reduced sulfur in underground water, calcium magnesium hardness and part microorganism, and the reaction for follow-up palladium catalyst provides good environment;
The underground water polluted is flowed out by first step water outlet and enters sand filtration unit after iron anode pretreatment unit, and underground water now also remainder iron throw out is retained by the granule filter material of filling in sand filtration container; Eliminate material poisonous to palladium catalyst in underground water, and in underground water, dissolve in hydrogen;
After sand filtration unit, when underground water flows into palladium-catalyzed reaction unit from second stage water outlet, water pollutant reduction in underground is removed efficiently by solubilised state hydrogen under palladium chtalyst effect, and the water after process flows out from treated water outlet;
Step (6), organic concentration level in monitoring process after purification water out, carry out energy optimization according to underground water repairing effect, adopt and feed water flow speed is regulated, or adjustments optimization energy consumption is carried out to total current.
2. the groundwater remediation method of iron anode coupling palladium chtalyst hydrogenation according to claim 1, it is characterized in that: iron anode pretreatment unit, sand filtration unit and palladium-catalyzed reaction unit in the device of the groundwater remediation that step is (1) described, three unit are indispensable, and are linked in sequence.
3. the groundwater remediation method of iron anode coupling palladium chtalyst hydrogenation according to claim 1, is characterized in that: the direct supply arranged in the iron anode pretreatment unit that step is (2) described contains two reometers, and two reometers connect two anodes respectively.
4. the groundwater remediation method of iron anode coupling palladium chtalyst hydrogenation according to claim 1, it is characterized in that: the distance of installing between electrode in the iron anode pretreatment unit that step is (2) described is 0.5 ~ 10cm, design spacing between electrodes is little, make the resistance that formed between electrode little, be conducive to reducing power consumption.
5. the groundwater remediation method of iron anode according to claim 1 coupling palladium chtalyst hydrogenation, is characterized in that: the (2) described control of step is 1 ︰ 1 ~ 2 ︰ 1 by the current ratio of iron anode and anode I.
6. the groundwater remediation method of iron anode according to claim 1 coupling palladium chtalyst hydrogenation, is characterized in that: the (3) described granule filter material of step is diameter 0.5 ~ 5mm quartz sand or coal particle.
7. the groundwater remediation method of iron anode according to claim 1 coupling palladium chtalyst hydrogenation, is characterized in that: the (4) described palladium catalyst of step selects aluminum oxide or the activated carbon particle of commercially available load palladium.
8. the groundwater remediation method of iron anode according to claim 1 coupling palladium chtalyst hydrogenation, 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, when Pollutant levels in treated water outlet are lower than the standard of setting, then improve water-in water flow velocity, otherwise then reduce water-in water flow velocity, make pollutent have enough residence time at palladium-catalyzed reaction unit, ensure treated water outlet place water quality reaching standard;
2. total current is regulated, if groundwater intake place reduced sulfur and calcium ions and magnesium ions concentration are higher than the standard of setting, then improve total current, otherwise then reduce total current, to ensure that palladium catalyst does not lose activity and reduces power consumption.
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| CN103318992A (en) * | 2013-07-08 | 2013-09-25 | 中国地质大学（武汉） | Double-anode electric flocculation arsenic removing method |
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