CN103936115B - A kind of three-dimensional electric Fenton water treatment method - Google Patents

A kind of three-dimensional electric Fenton water treatment method Download PDF

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CN103936115B
CN103936115B CN201410201495.4A CN201410201495A CN103936115B CN 103936115 B CN103936115 B CN 103936115B CN 201410201495 A CN201410201495 A CN 201410201495A CN 103936115 B CN103936115 B CN 103936115B
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water
electrode plate
porous electrode
fenton
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CN103936115A (en
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朱云庆
王传义
殷娇
王朋磊
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The present invention relates to a kind of three-dimensional electric Fenton water treatment method, the device related in the method is by reactor, porous electrode plate, activated carbon supported zero-valent metal fenton catalyst, water outlet, water-in, positive electrode and negative potential composition, with three-dimensional electricity strengthening Fenton oxidation method for core, by reaction unit, conversion zone is divided into positive electrode electricity Fenton oxidation district and negative potential ion reduction district, electrode materials is by activated carbon supported zero-valent metal iron, nickel, copper, cobalt, platinum, silver or palladium, intake through positive electrode electricity Fenton oxidation district, under the effect of electric field, digestion of metallic ion forming 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, negative potential reaction zone also can produce hydrogen peroxide by oxygen aeration, reduces additional hydrogen peroxide consumption.The result for the treatment of of dyeing and printing shows: adopt the method for the invention, can significantly improve colourity and COD in dyeing waste water crremoval efficiency, make water outlet reach National Industrial waste water recycling standard.

Description

A kind of three-dimensional electric Fenton water treatment method
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 removes organic pollutant, is with a wide range of applications.Current Fenton technology is mainly divided into homogeneous phase Fenton oxidation technology and heterogeneous Fenton oxidation technology according to the type of adopted catalyzer, and wherein the oxidation capacity of homogeneous phase Fenton oxidation technology is strong, processing efficiency is high, but the most important shortcoming Fe that to be reaction needed a large amount of 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 oxide carriedly realize at carrier surface the object reducing iron ion stripping, but the efficiency of the heterogeneous fenton catalyst up to the present, researched and developed still can not meet the demand of industrial application.Therefore how can development of new Fenton oxidation technology, both kept the Strong oxdiative ability of homogeneous phase Fenton oxidation technology, the discharge that can reduce again iron ion is significant for development Fenton catalytic oxidation technologies, 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 related in the method is by reaction unit, porous electrode plate, activated carbon supported zero-valent metal fenton catalyst, water outlet, water-in, positive electrode and negative potential composition, with three-dimensional electricity strengthening Fenton oxidation method for core, by reaction unit design, conversion zone is divided into positive electrode electricity Fenton oxidation district and negative potential ion reduction district, activated carbon supported zero-valent metal fenton catalyst is mainly by activated carbon supported zero-valent metal iron, nickel, cobalt, platinum, silver or palladium, intake through positive electrode electricity Fenton oxidation district, under the effect of electric field, digestion of metallic ion forming 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 reducing metal ions is become to have the low price ion of 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 related in the method is made up of reactor, porous electrode plate, activated carbon supported zero-valent metal fenton catalyst, water outlet, water-in, positive electrode and negative potential, and concrete operations follow these steps to carry out:
A, be coconut husk by raw material, apricot shell, refinery coke, coal or coal tar activated carbon granule, powder or the column prepared carry out drying for standby after pickling, washing, preparation zero-valent metal solution, gac is added in zero-valent metal solution, after stirring 2h, standing sedimentation, remove supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, the porous electrode plate (2) of impartial arrangement is provided with in reactor (1), be placed with activated carbon supported zero-valent metal fenton catalyst (3) between porous electrode plate (2), the sidewall of reactor (1) is fixed positive electrode (7) and negative potential (6) respectively, positive electrode (7) is connected to form oxidation zone with the porous electrode plate (2) of lower floor in reactor (1), negative potential (6) is connected to form reduction zone with the porous electrode plate (2) on reactor (1) upper strata, the top of reactor (1) is water outlet (4), the bottom of reactor (1) is water-in (5),
C, the oxygenizement of oxide regions utilizing positive electrode (7) to be connected with the porous electrode plate (2) of lower floor in reactor (1), the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor (1);
D, the reductive action of reduced zone utilizing negative potential (6) to be connected with the porous electrode plate (2) on upper strata in reactor (1), trap on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor (1);
E, injected after dyeing waste water and hydrogen peroxide mixing by reactor (1) bottom water-in (5) with constant flow pump, flow velocity is 0.5 L/h, regulates extra electric field voltage to be 2.5 V, detects colority of water, COD index;
F, to enter water COD be 300mg/L, and remove the colourity in water body completely, water outlet reaches National Industrial waste water recycling standard.
Activated carbon supported zero-valent metal fenton catalyst (3) in step a is have the iron of katalysis, nickel, copper, cobalt, platinum, silver or palladium to Fenton reagent.
Positive electrode (7) in step b in reactor (1) is connected to form oxidation zone with the porous electrode plate (2) of lower floor, negative potential (6) is connected to form reduction zone with the porous electrode plate (2) on upper strata, 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 step b in reactor (1) is 2 cm.
Porous electrode plate (2) described in step b is 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) reclaimed the metal ion in reaction system by negative potential reduction, reduce metal ion and discharge and expense needed for subsequent disposal; (4) the positive electrode electricity Fenton oxidation district of reacting and negative potential ion reduction district can regulate and control by changing extra electric field direction, can artificially adjust.
The arrangement in Zhong electricity Fenton oxidation district of the present invention and reducing metal ions district carries out regulating according to the actual needs in wastewater treatment process, staggered or segmentation arrangement array mode can be adopted, 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 electric Fenton oxidation district and reducing metal ions district by conversion zone, adopt activated carbon supported zero-valent metal as electrode materials, not only achieve the high-level efficiency of homogeneous phase Fenton's reaction system, and efficient recovery is realized to metal ion, overcome metal ion discharge bring environmental pollution, line clogging and aftertreatment cost up problem, be beneficial to and realize the application of Fenton oxidation technology in actual water technology.
The three-diemsnional electrode material used in the embodiment of the present invention is activated carbon supported zero-valent metal, and form electric Fenton oxidation district and reducing metal ions district 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 obtained 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 materials, those skilled in the art are also by additive method or approach, obtain the activated carbon supported zero-valent metal electrode materials of identical catalytic performance, thus 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 adopting the DSA electrode of other materials.
Accompanying drawing explanation
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, after stirring 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, be provided with the Ti/Sb-SnO of impartial arrangement in reactor 1 2porous electrode plate 2, Ti/Sb-SnO 2spacing between porous electrode plate 2 is 2 cm, at Ti/Sb-SnO 2be placed with step a between porous electrode plate 2 with the catalyzer 3 of activated carbon supported zero-valent metal iron, form the combination that is arranged above and below, the sidewall of reactor 1 fixes positive electrode 7 and negative potential 6 respectively, 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, in reactor 1, utilize electric field positive electrode 7 and Ti/Sb-SnO 2the oxygenizement of the oxide regions that porous electrode plate 2 connects, the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor 1;
D, in reactor 1, utilize electric field negative potential 6 and Ti/Sb-SnO 2the reductive action of reduced zone that porous electrode plate 2 connects, traps on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor 1;
E, with constant flow pump by dyeing waste water and hydrogen peroxide mixing after injected by water-in 5 bottom reactor 1, flow velocity is 0.5 L/h, extra electric field voltage is regulated to be 2.5 V, be under the Fenton oxidation effect of the catalyzer 3 of iron at the zero-valent metal that oxidation zone is activated carbon supported, generate hydroxyl radical free radical and oxygenolysis is carried out to organism, then through reduction zone, the metal ion of stripping is carried out reduction and reclaim, 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 waste water recycling standard, in equipment running process, when oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone exchange, the object reaching catalyst activation and run 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, after stirring 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, be provided with the titanium net porous electrode plate 2 of impartial arrangement in reactor 1, spacing between titanium net porous electrode plate 2 is 2 cm, step a is placed with the catalyzer 3 of activated carbon supported zero-valent metal cupric nitrate between titanium net porous electrode plate 2, formation is staggered combination, the sidewall of reactor 1 fixes positive electrode 7 and negative potential 6 respectively, positive electrode (7) and titanium net porous electrode plate 2 are connected to form oxidation zone, negative potential 6 and titanium net porous electrode plate 2 are connected to form reduction zone, the top of reactor 1 is water outlet 4, and the bottom of reactor 1 is water-in (5);
C, the oxygenizement of oxide regions utilizing electric field positive electrode 7 to be connected with titanium net porous electrode plate 2 in reactor 1, the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor 1;
D, the reductive action of reduced zone utilizing electric field negative potential 6 to be connected with titanium net porous electrode plate 2 in reactor 1, trap on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor 1;
E, with constant flow pump by dyeing waste water and hydrogen peroxide mixing after injected by water-in 5 bottom reactor 1, flow velocity is 0.5 L/h, extra electric field voltage is regulated to be 2.5 V, be under the Fenton oxidation effect of the catalyzer 3 of cupric nitrate at the zero-valent metal that oxidation zone is activated carbon supported, generate hydroxyl radical free radical and oxygenolysis is carried out to organism, then through reduction zone, the metal ion of stripping is carried out reduction and reclaim, 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 waste water recycling standard, in equipment running process, when oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone exchange, the object reaching catalyst activation and run 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, after stirring 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, be provided with the stainless steel plate porous electrode plate 2 of impartial arrangement in reactor 1, spacing between stainless steel plate porous electrode plate 2 is 2 cm, step a is placed with the catalyzer 3 of activated carbon supported zero-valent metal nickelous nitrate between stainless steel plate porous electrode plate 2, formation is arranged above and below combination, the sidewall of reactor 1 fixes positive electrode 7 and negative potential 6 respectively, positive electrode 7 and stainless steel porous electrode plate 2 are connected to form oxidation zone, negative potential 6 and stainless steel porous electrode plate 2 are connected to form reduction zone, the top of reactor 1 is water outlet 4, the bottom of reactor 1 is water-in (5),
C, the oxygenizement of oxide regions utilizing electric field positive electrode 7 to be connected with stainless steel plate porous electrode plate 2 in reactor 1, the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor 1;
D, the reductive action of reduced zone utilizing electric field negative potential 6 to be connected with stainless steel plate porous electrode plate 2 in reactor 1, trap on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor 1;
E, with constant flow pump by dyeing waste water and hydrogen peroxide mixing after injected by water-in 5 bottom reactor 1, flow velocity is 0.5 L/h, extra electric field voltage is regulated to be 2.5 V, be under the Fenton oxidation effect of the catalyzer 3 of nickelous nitrate at the zero-valent metal that oxidation zone is activated carbon supported, generate hydroxyl radical free radical and oxygenolysis is carried out to organism, then through reduction zone, the metal ion of stripping is carried out reduction and reclaim, 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 waste water recycling standard, in equipment running process, when oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone exchange, the object reaching catalyst activation and run continuously.
Embodiment 4
A, be that gac column prepared by coal carries 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, after stirring 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, be provided with the stainless (steel) wire porous electrode plate 2 of impartial arrangement in reactor 1, spacing between stainless (steel) wire porous electrode plate 2 is 2 cm, step a is placed with the catalyzer 3 of activated carbon supported zero-valent metal Silver Nitrate between stainless (steel) wire porous electrode plate 2, formation is arranged above and below combination, the sidewall of reactor 1 fixes positive electrode 7 and negative potential 6 respectively, positive electrode 7 and stainless (steel) wire porous electrode plate 2 are connected to form oxidation zone, negative potential 6 and stainless (steel) wire porous electrode plate 2 are connected to form reduction zone, the top of reactor 1 is water outlet 4, the bottom of reactor 1 is water-in 5,
C, the oxygenizement of oxide regions utilizing electric field positive electrode 7 to be connected with stainless (steel) wire porous electrode plate 2 in reactor 1, the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor 1;
D, the reductive action of reduced zone utilizing electric field negative potential 6 to be connected with stainless (steel) wire porous electrode plate 2 in reactor 1, trap on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor 1;
E, with constant flow pump by dyeing waste water and hydrogen peroxide mixing after injected by water-in 5 bottom reactor 1, flow velocity is 0.5 L/h, extra electric field voltage is regulated to be 2.5 V, be under the Fenton oxidation effect of the catalyzer 3 of Silver Nitrate at the zero-valent metal that oxidation zone is activated carbon supported, generate hydroxyl radical free radical and oxygenolysis is carried out to organism, then through reduction zone, the metal ion of stripping is carried out reduction and reclaim, 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 waste water recycling standard, in equipment running process, when oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone exchange, the object reaching catalyst activation and run 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, after stirring 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, be provided with the Ti/PbO of impartial arrangement in reactor 1 2porous electrode plate (2), Ti/PbO 2spacing between porous electrode plate (2) is 2 cm, at Ti/PbO 2be placed with step a between porous electrode plate 2 with the catalyzer 3 of activated carbon supported zero-valent metal rose vitriol, form the combination that is arranged above and below, the sidewall of reactor 1 fixes positive electrode 7 and negative potential 6 respectively, 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, in reactor 1, utilize electric field positive electrode 7 and Ti/PbO 2the oxygenizement of the oxide regions that porous electrode plate 2 connects, the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor 1;
D, in reactor 1, utilize electric field negative potential 6 and Ti/PbO 2the reductive action of reduced zone that porous electrode plate 2 connects, traps on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor 1;
E, with constant flow pump by dyeing waste water and hydrogen peroxide mixing after injected by water-in 5 bottom reactor 1, flow velocity is 0.5 L/h, extra electric field voltage is regulated to be 2.5 V, be under the Fenton oxidation effect of the catalyzer 3 of rose vitriol at the zero-valent metal that oxidation zone is activated carbon supported, generate hydroxyl radical free radical and oxygenolysis is carried out to organism, then through reduction zone, the metal ion of stripping is carried out reduction and reclaim, 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 waste water recycling standard, in equipment running process, when oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone exchange, the object reaching catalyst activation and run 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, after stirring 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, be provided with the titanium porous electrode plate 2 of impartial arrangement in reactor 1, spacing between titanium porous electrode plate 2 is 2 cm, step a is placed with the catalyzer 3 of activated carbon supported zero-valent metal chlorine platinum between titanium porous electrode plate 2, formation is arranged above and below combination, the sidewall of reactor 1 fixes positive electrode 7 and negative potential 6 respectively, positive electrode 7 and titanium plate porous electrode plate 2 are connected to form oxidation zone, negative potential 6 and titanium plate porous electrode plate 2 are connected to form reduction zone, the top of reactor 1 is water outlet (4), and the bottom of reactor 1 is water-in (5);
C, the oxygenizement of oxide regions utilizing electric field positive electrode 7 to be connected with titanium plate porous electrode plate 2 in reactor 1, the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor 1;
D, the reductive action of reduced zone utilizing electric field negative potential 6 to be connected with titanium plate porous electrode plate 2 in reactor 1, trap on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor 1;
E, with constant flow pump by dyeing waste water and hydrogen peroxide mixing after injected by water-in 5 bottom reactor 1, flow velocity is 0.5 L/h, extra electric field voltage is regulated to be 2.5 V, be under the Fenton oxidation effect of the catalyzer 3 of chlorine platinum at the zero-valent metal that oxidation zone is activated carbon supported, generate hydroxyl radical free radical and oxygenolysis is carried out to organism, then through reduction zone, the metal ion of stripping is carried out reduction and reclaim, 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 waste water recycling standard, in equipment running process, when oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone exchange, the object reaching catalyst activation and run 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, after stirring 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, be provided with the Ti/Sb-SnO of impartial arrangement in reactor 1 2porous electrode plate 2, Ti/Sb-SnO 2spacing between porous electrode plate 2 is 2 cm, at Ti/Sb-SnO 2be placed with step a between porous electrode plate 2 with the catalyzer 3 of activated carbon supported zero-valent metal chlorine palladium, form the combination that is staggered, the sidewall of reactor 1 fixes positive electrode 7 and negative potential 6 respectively, 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, in reactor 1, utilize electric field positive electrode 7 and Ti/Sb-SnO 2the oxygenizement of the oxide regions that porous electrode plate 2 connects, the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor 1;
D, in reactor 1, utilize electric field negative potential 6 and Ti/Sb-SnO 2the reductive action of reduced zone that porous electrode plate 2 connects, traps on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor 1;
E, with constant flow pump by dyeing waste water and hydrogen peroxide mixing after injected by water-in 5 bottom reactor 1, flow velocity is 0.5 L/h, extra electric field voltage is regulated to be 2.5 V, be under the Fenton oxidation effect of the catalyzer 3 of chlorine palladium at the zero-valent metal that oxidation zone is activated carbon supported, generate hydroxyl radical free radical and oxygenolysis is carried out to organism, then through reduction zone, the metal ion of stripping is carried out reduction and reclaim, 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 waste water recycling standard, in equipment running process, when oxidation zone catalyst deactivation, enter to note direction by conversion extra electric field and waste water, realize oxidation zone and reduction zone exchange, the object reaching catalyst activation and run continuously.

Claims (5)

1. the electric Fenton water treatment method of three-dimensional, it is characterized in that the device related in the method is made up of reactor, porous electrode plate, activated carbon supported zero-valent metal fenton catalyst, 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, the activated carbon granule that coal or coal tar are prepared respectively, powder or column carry out pickling, the rear drying for standby of washing, preparation zero-valent metal solution, gac is added in zero-valent metal solution, after stirring 2h, standing sedimentation, removes supernatant liquor, add pure water 50 mL wash and repeat 3 times, by the gac after load in temperature 120 DEG C of dryings, dried gac is carried out in nitrogen atmosphere reduction furnace temperature 300 DEG C of nitrogen atmosphere reduction, be stored in dustless experiment table for subsequent use;
B, the porous electrode plate (2) of impartial arrangement is provided with in reactor (1), be placed with activated carbon supported zero-valent metal fenton catalyst (3) between porous electrode plate (2), the sidewall of reactor (1) is fixed positive electrode (7) and negative potential (6) respectively, positive electrode (7) is connected to form oxidation zone with the porous electrode plate (2) of lower floor in reactor (1), negative potential (6) and reactor (1) porous electrode plate (2) are at the middle and upper levels connected to form reduction zone, the top of reactor (1) is water outlet (4), the bottom of reactor (1) is water-in (5),
C, the oxygenizement of oxide regions utilizing positive electrode (7) to be connected with the porous electrode plate (2) of lower floor in reactor (1), the stripping of reinforced metal ion, forms homogeneous phase Fenton's reaction system in reactor (1);
D, the reductive action of reduced zone utilizing negative potential (6) to be connected with the porous electrode plate (2) on upper strata in reactor (1), trap on cathodic activity high-area carbon by the metal ion in-situ reducing in the reaction system in reactor (1);
E, injected after dyeing waste water and hydrogen peroxide mixing by reactor (1) bottom water-in (5) with constant flow pump, flow velocity is 0.5 L/h, regulates extra electric field voltage to be 2.5 V, detects colority of water, COD index;
F, to enter water COD be 300mg/L, and remove the colourity in water body completely, water outlet reaches National Industrial waste water recycling standard.
2. method according to claim 1, the activated carbon supported zero-valent metal fenton catalyst (3) that it is characterized in that in step a is have the iron of katalysis, nickel, copper, cobalt, platinum, silver or palladium 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 the porous electrode plate (2) of lower floor, negative potential (6) is connected to form reduction zone with the porous electrode plate (2) on upper strata, 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 titanium plate, titanium net, stainless steel plate, stainless (steel) wire, Ti/Sb-SnO 2electrode or Ti/PbO 2electrode.
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