CN103936115A - Three-dimensional electro-fenton water treatment method - Google Patents
Three-dimensional electro-fenton water treatment method Download PDFInfo
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- CN103936115A CN103936115A CN201410201495.4A CN201410201495A CN103936115A CN 103936115 A CN103936115 A CN 103936115A CN 201410201495 A CN201410201495 A CN 201410201495A CN 103936115 A CN103936115 A CN 103936115A
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Abstract
The invention relates to a three-dimensional electro-fenton water treatment method. According to the method, an involved device comprises a reactor, a porous electrode plate, an active carbon loaded zero-valent metal fenton catalyst, a water outlet, a water inlet, a positive electrode and a negative electrode; a reaction area is divided into a positive electrode electro-fenton oxidation area and a negative electrode ion reduction area through a reaction device by taking a three-dimensional intensifying electro-fenton oxidation method as a kernel, an electrode material comprises active carbon loaded zero-valent metal ion, nickel, copper, cobalt, platinum and silver or palladium, inlet water passes through the positive electrode electro-fenton oxidation area, metal ions are digested under the action of an electric field to form an area high-concentration ion solution to intensify homogeneous-phase fenton reaction; a reacted water body enters a negative pole reduction area, and the metal ions contained in the solution are reduced to a cathodic active carbon electrode for recovery; and the negative electrode ion reaction area can generate hydrogen peroxide through oxygen aeration, so that the usage amount of added hydrogen peroxide is reduced. A dyeing waste water treatment result indicates that the method disclosed by the invention can outstandingly increase the chrominance and removal efficiency of CODCr (Chemical Oxygen Demand) of dyeing waste water and achieves the national industrial waste water recycling standard of effluent water.
Description
Technical field
The invention belongs to technical field of waste water processing, relate to a kind of three-dimensional electric Fenton water treatment method.
Background technology
Fenton oxidation technology is the High-efficient Water treatment technology that a kind of Quick Oxidation is removed organic pollutant, is with a wide range of applications.Fenton technology is mainly divided into homogeneous phase Fenton oxidation technology and heterogeneous Fenton oxidation technology according to the type of adopted catalyzer at present, and wherein the oxidation capacity of homogeneous phase Fenton oxidation technology is strong, processing efficiency is high, but most important shortcoming is a large amount of Fe of reaction needed
2+, need subsequent disposal, produce a large amount of iron containing sludges; In order to address this problem, develop again heterogeneous Fenton oxidation technology, by by active ingredient or the oxide carried object that reduces iron ion stripping that realizes at carrier surface, but the efficiency of the heterogeneous Fenton catalyzer of up to the present, researching and developing still can not meet the demand of industrial application.Therefore how can development of new Fenton oxidation technology, both kept the strong oxidation capacity of homogeneous phase Fenton oxidation technology, the discharge that can reduce again iron ion is significant for development Fenton catalyzed oxidation technology, has a good application prospect.
Summary of the invention
The object of the invention is, a kind of three-dimensional electric Fenton water treatment method is provided, the device relating in the method is by reaction unit, porous electrode plate, activated carbon supported zero-valent metal Fenton catalyzer, water outlet, water-in, positive electrode and negative potential composition, taking three-dimensional electricity strengthening Fenton oxidation method as core, design conversion zone is divided into positive electrode electricity Fenton oxidation district and negative potential ion reduction zone by reaction unit, electrode materials is mainly by activated carbon supported zero-valent metal iron, nickel, cobalt, platinum, silver or palladium, water inlet is through positive electrode electricity Fenton oxidation district, under the effect of electric field, digestion of metallic ion forms region high concentration ion solution, strengthening homogeneous phase Fenton's reaction, after reaction, water body enters negative potential reduction zone, and the metal ion in solution is restored on cathodic activity carbon electrode and reclaims, simultaneous reactions region intermediate can arrange low voltage negative potential reduction zone, oxidized metal ion is reduced into the low price ion with catalytic activity, proceeds follow-up Fenton's reaction, negative potential reaction zone also can produce hydrogen peroxide by oxygen aeration, reduces additional hydrogen peroxide consumption.
The three-dimensional electric Fenton water treatment method of one of the present invention, the device relating in the method is made up of reactor, porous electrode plate, activated carbon supported zero-valent metal Fenton catalyzer, water outlet, water-in, positive electrode and negative potential, and concrete operations follow these steps to carry out:
A, be that activated carbon granule, powder or column prepared by coconut husk, apricot shell, refinery coke, coal or coal tar are carried out drying for standby after pickling, washing by raw material, preparation zero-valent metal solution, gac is added in zero-valent metal solution, stir after 2h, standing sedimentation, remove supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor (1), be provided with the impartial porous electrode plate (2) of arranging, between porous electrode plate (2), be placed with the catalyzer (3) with activated carbon supported zero-valent metal, on the sidewall of reactor (1), fix respectively positive electrode (7) and negative potential (6), positive electrode (7) is connected to form oxidation zone with porous electrode plate (2), negative potential (6) is connected to form reduction zone with porous electrode plate (2), the top of reactor (1) is water outlet (4), and the bottom of reactor (1) is water-in (5);
C, in reactor (1), utilize the oxygenizement of the oxide regions that electric field positive electrode (7) is connected with porous electrode plate (2), the stripping of reinforced metal ion forms homogeneous phase Fenton's reaction system in reactor (1);
D, in reactor (1), utilize the reductive action of the reduced zone that electric field negative potential (6) is connected with porous electrode plate (2), by the metal ion in-situ reducing in the reaction system in reactor (1) and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor (1) bottom water-in (5) after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, detects colority of water, COD index;
F, to enter water COD be 300mg/L, removes the colourity in water body completely, and water outlet reaches national industrial effluent reusing standard.
The catalyzer (3) of the zero-valent metal in step a is for having iron, nickel, copper, cobalt, platinum, silver or the palladium of katalysis to Fenton reagent.
Positive electrode (7) in reactor in step b (1) is connected to form oxidation zone with porous electrode plate (2), and negative potential (6) is connected to form reduction zone with porous electrode plate (2), and oxidation zone and reduction zone are combination or the combination that is staggered of being arranged above and below.
Porous electrode plate (2) spacing in reactor in step b (1) is 2 cm.
Positive electrode described in step b (7) and negative potential (6) are titanium plate, titanium net, stainless steel plate, stainless (steel) wire, Ti/Sb-SnO
2electrode or Ti/PbO
2electrode.
The three-dimensional electric Fenton water treatment method of one of the present invention, the feature of the three-dimensional point strengthening Fenton oxidation technology of the method mainly contains: (1), by electric field action, realizes electricity strengthening homogeneous phase Fenton's reaction, improves reaction efficiency; (2) negative potential reduction zone can Effective Regulation reducing power, the removal efficiency of strengthening Fenton's reaction; (3) reduce and reclaim the metal ion in reaction system by negative potential, reduce metal ion and discharge and the required expense of subsequent disposal; (4) positive electrode of reaction electricity Fenton oxidation district and negative potential ion reduction zone can regulate and control by changing extra electric field direction, can artificially adjust.
Arranging of Zhong electricity Fenton oxidation district of the present invention and metal ion reduction zone is that actual needs according in wastewater treatment process regulates, can adopt the staggered or segmentation array mode of arranging, the technical scheme that those skilled in the art can provide according to the invention process case, obtain technology enlightenment, adopt different arrangement methods, reach same technique effect.
Beneficial effect: the three-dimensional electricity Fenton water treatment method described in the present invention, the method is by being divided into conversion zone electric Fenton oxidation district and metal ion reduction zone, adopt activated carbon supported zero-valent metal as electrode materials, not only realize the high-level efficiency of homogeneous phase Fenton's reaction system, and metal ion is realized to efficient recovery, overcome the problem that metal ion discharges environmental pollution, line clogging and the aftertreatment cost up brought, be beneficial to and realize the application of Fenton oxidation technology in actual water technology.
The three-diemsnional electrode material using in the embodiment of the present invention is activated carbon supported zero-valent metal, and form electric Fenton oxidation district and metal ion reduction zone by the effect of electric field, the three-dimensional electro-Fenton reaction system of final formation, infers: thus when three-diemsnional electrode material adopts other conductive carriers (as quartz sand load SnO
2material etc.) time, also can realize technique effect of the present invention.
Activated carbon supported zero-valent metal in the embodiment of the present invention is to make by the method for co-precipitation+nitrogen atmosphere reduction, these class methods belong to the conventional using method that those skilled in the art grasp, be widely used in and prepare supported catalyst agent material, those skilled in the art also can pass through additive method or approach, obtain the activated carbon supported zero-valent metal electrode materials of identical catalytic performance, thereby realize technique effect of the present invention.
Porous electrode plate in the embodiment of the present invention is titanium plate, titanium net, stainless steel plate, stainless (steel) wire, Ti/Sb-SnO
2electrode or Ti/PbO
2electrode, wherein Ti/Sb-SnO
2electrode and Ti/PbO
2electrode is the conventional DSA electrode that those skilled in the art grasp, and is widely used in electrocatalysis water technology, and those skilled in the art also can realize technique effect of the present invention by the DSA electrode that adopts other materials.
Brief description of the drawings
Fig. 1 reaction unit structural representation of the present invention.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way;
Embodiment 1
A, be that activated carbon granule prepared by coconut husk carries out drying for standby after pickling, washing by raw material, the iron nitrate solution of preparation zero-valent metal 0.05 mol/L, the gac of drying for standby is added in iron nitrate solution, stir after 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor 1, be provided with the impartial Ti/Sb-SnO arranging
2porous electrode plate 2, Ti/Sb-SnO
2spacing between porous electrode plate 2 is 2 cm, at Ti/Sb-SnO
2between porous electrode plate 2, be placed with the catalyzer 3 of step a with activated carbon supported zero-valent metal iron, form the combination that is arranged above and below, on the sidewall of reactor 1, fix respectively positive electrode 7 and negative potential 6, positive electrode 7 and Ti/Sb-SnO
2porous electrode plate 2 is connected to form oxidation zone, negative potential 6 and Ti/Sb-SnO
2porous electrode plate 2 is connected to form reduction zone, and the top of reactor 1 is water outlet 4, and the bottom of reactor 1 is water-in 5;
C, at interior electric field positive electrode 7 and the Ti/Sb-SnO of utilizing of reactor 1
2the oxygenizement of the oxide regions that porous electrode plate 2 connects, the stripping of reinforced metal ion, in the interior formation homogeneous phase of reactor 1 Fenton's reaction system;
D, at interior electric field negative potential 6 and the Ti/Sb-SnO of utilizing of reactor 1
2the reductive action of the reduced zone that porous electrode plate 2 connects, by the metal ion in-situ reducing in the reaction system in reactor 1 and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor 1 bottom water-in 5 after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, under the Fenton oxidation effect of the catalyzer 3 that is iron at the activated carbon supported zero-valent metal of oxidation zone, generate hydroxyl radical free radical organism is carried out to oxygenolysis, then through reduction zone, the metal ion of stripping is reduced to recovery, detect colority of water, COD index;
F, to enter water COD be 300mg/L, remove the colourity in water body completely, water outlet reaches national industrial effluent reusing standard, in equipment running process, in the time of oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone and exchange, the object that reaches catalyst activation and move continuously.
Embodiment 2
A, be that activated carbon granule prepared by apricot shell carries out drying for standby after pickling, washing by raw material, the copper nitrate solution of preparation zero-valent metal 0.05 mol/L, the gac of drying for standby is added in copper nitrate solution, stir after 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor 1, be provided with the impartial titanium net porous electrode plate 2 of arranging, spacing between titanium net porous electrode plate 2 is 2 cm, between titanium net porous electrode plate 2, be placed with the catalyzer 3 of step a with activated carbon supported zero-valent metal cupric nitrate, the formation combination that is staggered, on the sidewall of reactor 1, fix respectively positive electrode 7 and negative potential 6, positive electrode (7) is connected to form oxidation zone with titanium net porous electrode plate 2, negative potential 6 is connected to form reduction zone with titanium net porous electrode plate 2, the top of reactor 1 is water outlet 4, and the bottom of reactor 1 is water-in (5);
C, in the interior oxygenizement of utilizing the oxide regions that electric field positive electrode 7 is connected with titanium net porous electrode plate 2 of reactor 1, the stripping of reinforced metal ion, in the interior formation homogeneous phase of reactor 1 Fenton's reaction system;
D, in the interior reductive action of utilizing the reduced zone that electric field negative potential 6 is connected with titanium net porous electrode plate 2 of reactor 1, by the metal ion in-situ reducing in the reaction system in reactor 1 and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor 1 bottom water-in 5 after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, under the Fenton oxidation effect of the catalyzer 3 that is cupric nitrate at the activated carbon supported zero-valent metal of oxidation zone, generate hydroxyl radical free radical organism is carried out to oxygenolysis, then through reduction zone, the metal ion of stripping is reduced to recovery, detect colority of water, COD index;
F, to enter water COD be 300mg/L, remove the colourity in water body completely, water outlet reaches national industrial effluent reusing standard, in equipment running process, in the time of oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone and exchange, the object that reaches catalyst activation and move continuously.
Embodiment 3
A, be that absorbent charcoal powder body prepared by refinery coke carries out drying for standby after pickling, washing by raw material, the nickel nitrate solution of preparation zero-valent metal 0.05 mol/L, the gac of drying for standby is added in nickel nitrate solution, stir after 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor 1, be provided with the impartial stainless steel plate porous electrode plate 2 of arranging, spacing between stainless steel plate porous electrode plate 2 is 2 cm, between stainless steel plate porous electrode plate 2, be placed with the catalyzer 3 of step a with activated carbon supported zero-valent metal nickelous nitrate, the formation combination that is arranged above and below, on the sidewall of reactor 1, fix respectively positive electrode 7 and negative potential 6, positive electrode 7 is connected to form oxidation zone with stainless steel porous electrode plate 2, negative potential 6 is connected to form reduction zone with stainless steel porous electrode plate 2, the top of reactor 1 is water outlet 4, the bottom of reactor 1 is water-in (5),
C, in the interior oxygenizement of utilizing the oxide regions that electric field positive electrode 7 is connected with stainless steel plate porous electrode plate 2 of reactor 1, the stripping of reinforced metal ion, in the interior formation homogeneous phase of reactor 1 Fenton's reaction system;
D, in the interior reductive action of utilizing the reduced zone that electric field negative potential 6 is connected with stainless steel plate porous electrode plate 2 of reactor 1, by the metal ion in-situ reducing in the reaction system in reactor 1 and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor 1 bottom water-in 5 after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, under the Fenton oxidation effect of the catalyzer 3 that is nickelous nitrate at the activated carbon supported zero-valent metal of oxidation zone, generate hydroxyl radical free radical organism is carried out to oxygenolysis, then through reduction zone, the metal ion of stripping is reduced to recovery, detect colority of water, COD index;
F, to enter water COD be 300mg/L, remove the colourity in water body completely, water outlet reaches national industrial effluent reusing standard, in equipment running process, in the time of oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone and exchange, the object that reaches catalyst activation and move continuously.
Embodiment 4
A, be that gac column prepared by coal is carried out drying for standby after pickling, washing by raw material, the silver nitrate solution of preparation zero-valent metal 0.05 mol/L, the gac of drying for standby is added in silver nitrate solution, stir after 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor 1, be provided with the impartial stainless (steel) wire porous electrode plate 2 of arranging, spacing between stainless (steel) wire porous electrode plate 2 is 2 cm, between stainless (steel) wire porous electrode plate 2, be placed with the catalyzer 3 of step a with activated carbon supported zero-valent metal Silver Nitrate, the formation combination that is arranged above and below, on the sidewall of reactor 1, fix respectively positive electrode 7 and negative potential 6, positive electrode 7 is connected to form oxidation zone with stainless (steel) wire porous electrode plate 2, negative potential 6 is connected to form reduction zone with stainless (steel) wire porous electrode plate 2, the top of reactor 1 is water outlet 4, the bottom of reactor 1 is water-in 5,
C, in the interior oxygenizement of utilizing the oxide regions that electric field positive electrode 7 is connected with stainless (steel) wire porous electrode plate 2 of reactor 1, the stripping of reinforced metal ion, in the interior formation homogeneous phase of reactor 1 Fenton's reaction system;
D, in the interior reductive action of utilizing the reduced zone that electric field negative potential 6 is connected with stainless (steel) wire porous electrode plate 2 of reactor 1, by the metal ion in-situ reducing in the reaction system in reactor 1 and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor 1 bottom water-in 5 after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, under the Fenton oxidation effect of the catalyzer 3 that is Silver Nitrate at the activated carbon supported zero-valent metal of oxidation zone, generate hydroxyl radical free radical organism is carried out to oxygenolysis, then through reduction zone, the metal ion of stripping is reduced to recovery, detect colority of water, COD index;
F, to enter water COD be 300mg/L, remove the colourity in water body completely, water outlet reaches national industrial effluent reusing standard, in equipment running process, in the time of oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone and exchange, the object that reaches catalyst activation and move continuously.
Embodiment 5
A, be that activated carbon granule prepared by coal tar carries out drying for standby after pickling, washing by raw material, the cobalt sulfate solution of preparation zero-valent metal 0.05 mol/L, the gac of drying for standby is added in cobalt sulfate solution, stir after 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor 1, be provided with the impartial Ti/PbO arranging
2porous electrode plate (2), Ti/PbO
2spacing between porous electrode plate (2) is 2 cm, at Ti/PbO
2between porous electrode plate 2, be placed with the catalyzer 3 of step a with activated carbon supported zero-valent metal rose vitriol, form the combination that is arranged above and below, on the sidewall of reactor 1, fix respectively positive electrode 7 and negative potential 6, positive electrode 7 and Ti/PbO
2porous electrode plate 2 is connected to form oxidation zone, negative potential 6 and Ti/PbO
2porous electrode plate 2 is connected to form reduction zone, and the top of reactor 1 is water outlet 4, and the bottom of reactor 1 is water-in 5;
C, at interior electric field positive electrode 7 and the Ti/PbO of utilizing of reactor 1
2the oxygenizement of the oxide regions that porous electrode plate 2 connects, the stripping of reinforced metal ion, in the interior formation homogeneous phase of reactor 1 Fenton's reaction system;
D, at interior electric field negative potential 6 and the Ti/PbO of utilizing of reactor 1
2the reductive action of the reduced zone that porous electrode plate 2 connects, by the metal ion in-situ reducing in the reaction system in reactor 1 and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor 1 bottom water-in 5 after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, under the Fenton oxidation effect of the catalyzer 3 that is rose vitriol at the activated carbon supported zero-valent metal of oxidation zone, generate hydroxyl radical free radical organism is carried out to oxygenolysis, then through reduction zone, the metal ion of stripping is reduced to recovery, detect colority of water, COD index;
F, to enter water COD be 300mg/L, remove the colourity in water body completely, water outlet reaches national industrial effluent reusing standard, in equipment running process, in the time of oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone and exchange, the object that reaches catalyst activation and move continuously.
Embodiment 6
A, be that activated carbon granule prepared by coconut husk carries out drying for standby after pickling, washing by raw material, the platinum acid chloride solution of preparation zero-valent metal 0.05 mol/L, the gac of drying for standby is added in platinum acid chloride solution, stir after 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor 1, be provided with the impartial titanium porous electrode plate 2 of arranging, spacing between titanium porous electrode plate 2 is 2 cm, between titanium porous electrode plate 2, be placed with the catalyzer 3 of step a with activated carbon supported zero-valent metal chlorine platinum, the formation combination that is arranged above and below, on the sidewall of reactor 1, fix respectively positive electrode 7 and negative potential 6, positive electrode 7 is connected to form oxidation zone with titanium plate porous electrode plate 2, negative potential 6 is connected to form reduction zone with titanium plate porous electrode plate 2, the top of reactor 1 is water outlet (4), and the bottom of reactor 1 is water-in (5);
C, in the interior oxygenizement of utilizing the oxide regions that electric field positive electrode 7 is connected with titanium plate porous electrode plate 2 of reactor 1, the stripping of reinforced metal ion, in the interior formation homogeneous phase of reactor 1 Fenton's reaction system;
D, in the interior reductive action of utilizing the reduced zone that electric field negative potential 6 is connected with titanium plate porous electrode plate 2 of reactor 1, by the metal ion in-situ reducing in the reaction system in reactor 1 and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor 1 bottom water-in 5 after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, be under the Fenton oxidation effect of catalyzer 3 of chlorine platinum at the activated carbon supported zero-valent metal of oxidation zone, generate hydroxyl radical free radical organism is carried out to oxygenolysis, then through reduction zone, the metal ion of stripping is reduced to recovery, detect colority of water, COD index;
F, to enter water COD be 300mg/L, remove the colourity in water body completely, water outlet reaches national industrial effluent reusing standard, in equipment running process, in the time of oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone and exchange, the object that reaches catalyst activation and move continuously.
Embodiment 7
A, be that absorbent charcoal powder body prepared by apricot shell carries out drying for standby after pickling, washing by raw material, the chlorine palladium acid solution of preparation zero-valent metal 0.05 mol/L, the gac of drying for standby is added in chlorine palladium acid solution, stir after 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor 1, be provided with the impartial Ti/Sb-SnO arranging
2porous electrode plate 2, Ti/Sb-SnO
2spacing between porous electrode plate 2 is 2 cm, at Ti/Sb-SnO
2between porous electrode plate 2, be placed with the catalyzer 3 of step a with activated carbon supported zero-valent metal chlorine palladium, form the combination that is staggered, on the sidewall of reactor 1, fix respectively positive electrode 7 and negative potential 6, positive electrode 7 and Ti/Sb-SnO
2porous electrode plate 2 is connected to form oxidation zone, negative potential 6 and Ti/Sb-SnO
2porous electrode plate 2 is connected to form reduction zone, and the top of reactor 1 is water outlet 4, and the bottom of reactor 1 is water-in 5;
C, at interior electric field positive electrode 7 and the Ti/Sb-SnO of utilizing of reactor 1
2the oxygenizement of the oxide regions that porous electrode plate 2 connects, the stripping of reinforced metal ion, in the interior formation homogeneous phase of reactor 1 Fenton's reaction system;
D, at interior electric field negative potential 6 and the Ti/Sb-SnO of utilizing of reactor 1
2the reductive action of the reduced zone that porous electrode plate 2 connects, by the metal ion in-situ reducing in the reaction system in reactor 1 and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor 1 bottom water-in 5 after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, be under the Fenton oxidation effect of catalyzer 3 of chlorine palladium at the activated carbon supported zero-valent metal of oxidation zone, generate hydroxyl radical free radical organism is carried out to oxygenolysis, then through reduction zone, the metal ion of stripping is reduced to recovery, detect colority of water, COD index;
F, to enter water COD be 300mg/L, remove the colourity in water body completely, water outlet reaches national industrial effluent reusing standard, in equipment running process, in the time of oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone and exchange, the object that reaches catalyst activation and move continuously.
Claims (5)
1. the electric Fenton water treatment method of three-dimensional, it is characterized in that the device relating in the method is made up of reactor, porous electrode plate, activated carbon supported zero-valent metal Fenton catalyzer, water outlet, water-in, positive electrode and negative potential, concrete operations follow these steps to carry out:
A, by commercially available coconut husk, apricot shell, refinery coke, coal or coal-tar base activated carbon granule, powder or column carry out pickling, washing after drying for standby, preparation zero-valent metal solution, gac is added in zero-valent metal solution, stir after 2h, standing sedimentation, remove supernatant liquor, add pure water 50 mL to wash and repeat 3 times, gac after load is dry 120 DEG C of temperature, dried gac is carried out in nitrogen atmosphere reduction furnace to 300 DEG C of nitrogen atmosphere reduction of temperature, be stored in dustless experiment table for subsequent use;
B, in reactor (1), be provided with the impartial porous electrode plate (2) of arranging, between porous electrode plate (2), be placed with the catalyzer (3) with activated carbon supported zero-valent metal, on the sidewall of reactor (1), fix respectively positive electrode (7) and negative potential (6), positive electrode (7) is connected to form oxidation zone with porous electrode plate (2), negative potential (6) is connected to form reduction zone with porous electrode plate (2), the top of reactor (1) is water outlet (4), and the bottom of reactor (1) is water-in (5);
C, in reactor (1), utilize the oxygenizement of the oxide regions that electric field positive electrode (7) is connected with porous electrode plate (2), the stripping of reinforced metal ion forms homogeneous phase Fenton's reaction system in reactor (1);
D, in reactor (1), utilize the reductive action of the reduced zone that electric field negative potential (6) is connected with porous electrode plate (2), by the metal ion in-situ reducing in the reaction system in reactor (1) and trap on cathodic activity charcoal carrier;
E, with constant flow pump will dyeing waste water and hydrogen peroxide injected by reactor (1) bottom water-in (5) after mixing, flow velocity is 0.5 L/h, regulating extra electric field voltage is 2.5 V, detects colority of water, COD index;
F, to enter water COD be 300mg/L, removes the colourity in water body completely, and water outlet reaches national industrial effluent reusing standard.
2. method according to claim 1, is characterized in that the catalyzer (3) of the zero-valent metal in step a is for having iron, nickel, copper, cobalt, platinum, silver or the palladium of katalysis to Fenton reagent.
3. method according to claim 1, it is characterized in that the positive electrode (7) in reactor in step b (1) is connected to form oxidation zone with porous electrode plate (2), negative potential (6) is connected to form reduction zone with porous electrode plate (2), and oxidation zone and reduction zone are combination or the combination that is staggered of being arranged above and below.
4. method according to claim 1, is characterized in that porous electrode plate (2) spacing in reactor in step b (1) is 2 cm.
5. according to the method described in claim 1, it is characterized in that the porous electrode plate (2) described in step b is for titanium plate, titanium net, stainless steel plate, stainless (steel) wire, Ti/Sb-SnO
2electrode or Ti/PbO
2electrode.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN107497422A (en) * | 2017-09-13 | 2017-12-22 | 安徽大学 | A kind of Pd/C catalyst and its biological preparation method applied to electric Fenton-like system negative electrode |
| CN110563093A (en) * | 2019-09-16 | 2019-12-13 | 南京工业大学 | Membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device and process |
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| CN112978872A (en) * | 2021-02-25 | 2021-06-18 | 西安建筑科技大学 | Rotating disc type three-dimensional electro-Fenton device for treating landfill leachate membrane concentrated solution |
| CN113716655A (en) * | 2021-09-10 | 2021-11-30 | 吉林建筑大学 | Ferronickel bimetal three-dimensional electrode particle filler and preparation method and application thereof |
| CN113716655B (en) * | 2021-09-10 | 2022-11-22 | 吉林建筑大学 | Ferronickel bimetal three-dimensional electrode particle filler and preparation method and application thereof |
| CN114392754A (en) * | 2022-02-07 | 2022-04-26 | 中国石油大学(北京) | Modified activated carbon fiber composite material, preparation method thereof, heterogeneous electro-Fenton catalytic composite material and application thereof |
| CN114392754B (en) * | 2022-02-07 | 2022-12-23 | 中国石油大学(北京) | Modified activated carbon fiber composite material, preparation method thereof, heterogeneous electro-Fenton catalytic composite material and application thereof |
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