CN201501809U - Biomass conductive carbon double-bed electrode reactor for treatment of low-concentration metallic wastewater - Google Patents
Biomass conductive carbon double-bed electrode reactor for treatment of low-concentration metallic wastewater Download PDFInfo
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- CN201501809U CN201501809U CN2009202357728U CN200920235772U CN201501809U CN 201501809 U CN201501809 U CN 201501809U CN 2009202357728 U CN2009202357728 U CN 2009202357728U CN 200920235772 U CN200920235772 U CN 200920235772U CN 201501809 U CN201501809 U CN 201501809U
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Abstract
The utility model discloses a biomass conductive carbon double-bed electrode reactor for treatment of low-concentration metallic wastewater, which comprises a wastewater purification reaction bed and a metal recovery reaction bed. The wastewater purification reaction bed comprises a purification reaction bed body, a wastewater channel, a fluidization distribution pipe and a first DC converter; and the metal recovery reaction bed comprises a metal recovery reaction bed body, an air chamber channel, a fluidization air duct and a second DC converter. Compared with the prior art, the utility model adopts the biomass conductive carbon to substitute the traditional metal particles or activated carbon, and simultaneously has the advantages of metal and activated carbon. On one hand, the utility model has excellent conductivity, and has a high current density when in used as the fluidized bed electrode reactor for formation of the conductive medium; on the other hand, since the specific surface area of the conductive carbon is large, the utility model has high adsorption capacity, and can absorb metal ions at first and then reduce the metal ions, thereby greatly improving the current efficiency and exerting particular effect on the low-concentration wastewater containing the metal ions.
Description
Technical field:
The utility model relates to a kind of method of handling the biomass conductive carbon double-fluidized-bed electrode device and the high efficiente callback metal of low-concentration metallic wastewater, is particularly suitable for handling that metal ion content is low, the costly trade effluent of metal recovery.The utility model belongs to the technical field of fluid-bed electrode electrochemical treatment trade effluent.
Background technology:
China's production prosperity, the quantity discharged of trade effluent occupies first of the whole world.Usually contain a large amount of metal ions in the trade effluent (as trade effluents such as metallurgy, plating, precious metal processing, printing and dyeing, process hides), as gold and silver, copper, lead, cadmium, chromium, zinc etc.Though the concentration of these metal ions in waste water is very low, but because it is to environment and human very harmful, before discharging, must carry out strict purifying treatment, and the recovery value of these metal ions is very high, is necessary very much development of new innoxious efficiently and resource utilization retrieving arrangement and method.
At present, process for treating industrial waste water mainly can be divided into four big classes: physics method, chemical method, biological process and physico-chemical processes.The physics method comprises that mainly the suspended state pollution substance separates (as removing degrease), evaporation concentration etc., and these methods are generally just as a link in other treatment processs.Chemical method is a current application method the most widely, it mainly is by add corresponding chemical agent in waste water, by chemical reaction pollutent is become harmless or hypotoxic material (as adding the hypochlorite oxidation cryanide ion, adding ferrous sulfate and hexavalent chrome reduction is become the less trivalent chromium of toxicity etc.), perhaps it is become easily with the isolating material of sewage after adopt physical method to remove (separating after with heavy metal precipitations such as copper, cadmium, chromium, lead) as adding yellow soda ash.This method is simple to operate, the facility investment expense is low, comparatively stable to the removal effect of high-concentration metallic ions, but after concentration of metal ions is reduced to a certain degree, further the effect of removing is very limited, in addition, also there is serious secondary pollution problem (as producing a large amount of poisonous and harmful mud, may introducing new pollutent etc.) in this method, the resource utilization weak effect is difficult to satisfy the emission request of increasingly stringent.Biological process is a vital movement process of utilizing microorganism, pollutants in waste water is shifted or transforms, as with decolouring bacillus anaerobic treatment chromate waste water, add active sludge treatment chromate waste water etc. with pseudomonas, but this method only limits to single bacterial strain and handles single pollutent, and it is very big disturbed by other pollutents, and decontamination effect improving is very unstable.Physico-chemical processes is the method that waste water is purified by physics and chemical comprehensive action, as ion exchange method, active carbon adsorption, electrochemical process etc.
Ion exchange method is that ion in the exchange resin and the heavy metal ion in the waste water are exchanged, reach the purpose of purifying waste water, its shortcoming is only some specific zwitterion to be had decontamination effect improving preferably, and especially easily by other contaminants in the sewage, add exchange resin price height, regeneration running cost height, the large-scale promotion difficulty is bigger.
Active carbon adsorption mainly is that the micropore that utilizes the activated carbon prosperity captures, absorb polluted matter (comprising heavy metal ion, solia particle, organism etc.), its shortcoming is very poor for the selectivity that removes of pollutent, be difficult to carry out recycling, add that the activated carbon consumption is big, regeneration effect is undesirable, the depleted activated carbon need be handled as danger wastes, has the potential secondary pollution.
Electrochemical process does not need to add any chemical agent, and flexible operation, flow process are simple, can not produce secondary pollution (as mud, waste residue etc.), can the higher metal (as gold and silver, copper, zinc etc.) of efficient recovery economic worth, so the electrochemical treatment method is known as the clean method again.Current electrochemical reaction appts mainly is divided into two kinds of plate electrode reactor and fluidization electrode reactors.The yin, yang electrode of plate electrode reactor is parallel flat board arranged in pairs, and in this device operational process, the pollutent concentration polarization is big, and current density is little (general can only to reach 200～300A/m at most
3), current efficiency low (the highest have only 80～85%).The fluidization electrode reactor is a chemical cell that yin, yang the two poles of the earth is separated by barrier film, in a half-cell (cathodic reaction zone), insert feeding electrode, add conductive particle (with the identical metallic particles of intending reclaiming of metal types) again, the bottom is provided with liquid distributing board, impel the particle in the reaction zone to be fluidized state, form the fluidization electrode.Between the cathodic reaction zone endoparticle and and feeding electrode between collision frequent, impel particle charged; The fluidization campaign of particle in cathodic reaction zone be accelerating liquid and intergranular rate of mass transfer greatly, and the concentration polarization of metal ion is reduced greatly, the current density of electrochemical reaction can be brought up to 1500～2500A/m
3, current efficiency is increased to more than 95%, and equipment volume greatly reduces.
Generally use metallic particles as fluidizing medium in the present fluid-bed electrode reactor, its specific surface area is minimum, does not have trapping ability for metal ion itself, is deposited on the metallic surface when relying on metal ion to be reduced into metal simple-substance fully.When concentration of metal ions is very low, the speed of metal ion reduce deposition is very slow, so conventional fluid-bed electrode ability aspect the processing of low-concentration metallic wastewater is very limited.
Summary of the invention
The major technique that the utility model solved is at above-mentioned the deficiencies in the prior art, and a kind of decontamination effect improving that improves the metal ion waste water of lower concentration is provided, and improves the biomass conductive carbon double-fluidized-bed electrode reactor of waste water reclamation metal purity simultaneously.
For solving the problems of the technologies described above, the technical solution adopted in the utility model is:
A kind of biomass conductive carbon double-fluidized-bed electrode reactor, comprise purification of waste water reaction bed and metal recovery reaction bed, described purification of waste water reaction bed comprises purification reaction bed bed body, the waste water header, the fluidisation distribution pipe and the first direct current transmodulator, be provided with the first insulation osmotic membrane on described purification reaction bed bed body, described purification reaction bed bed body is divided into purification of waste water anodic reaction district and purification of waste water cathodic reaction zone by the described first insulation osmotic membrane, in purification of waste water anodic reaction district, be provided with the outlet of anode and purification of waste water positive column, in the purification of waste water cathodic reaction zone, be provided with the cathode feed utmost point, biomass conductive carbon particle and the outlet of purification of waste water cathodic area, described anode is connected with the positive pole of the first direct current transmodulator, described negative electrode is connected with the negative pole of direct current transmodulator, on described purification reaction bed bed body, also be provided with fluidisation distribution pipe inlet, biomass conductive carbon particle inlet, the outlet of enriched in metals artifact matter conduction charcoal, described fluidisation distribution pipe links with described fluidisation distribution pipe inlet; Described metal recovery reaction bed comprises: metal recovery reaction bed bed body, the air compartment header, the fluidisation airduct and the second direct current transmodulator, be provided with the second insulation osmotic membrane on described metal recovery reaction bed bed body, described metal recovery reaction bed bed body is divided into metal recovery anodic reaction district and metal recovery cathodic reaction zone by the described second insulation osmotic membrane, in described metal recovery anodic reaction district, be provided with the anode feeding electrode, anodic reaction district pneumatic outlet, fluidizing medium entered the mouth after biomass conductive carbon reclaimed mouth and enriched in metals, the fluidizing medium inlet is connected with described enriched in metals artifact matter conduction charcoal outlet of drawing together the purification of waste water reaction bed after this enriched in metals, described metal recovery cathodic reaction zone is provided with the cathode feed utmost point, the outlet of recovery metal, reclaim fluidizing medium inlet and cathodic reaction zone pneumatic outlet, described anode feeding electrode is connected with the positive pole of the second direct current transmodulator, the described cathode feed utmost point is connected with the negative pole of the second direct current transmodulator, also be provided with the fluidized wind tube inlet on described metal recovery reaction bed bed body, described fluidisation airduct links with described fluidized wind tube inlet.
Described biomass conductive carbon reclaims mouth and is connected with described biomass conductive carbon particle inlet.
The base plate of described purification reaction bed bed body is the tilting grid distributor, and the biomass conductive carbon particle of tilting grid distributor after the enriched in metals artifact matter conduction charcoal exit of purification of waste water cathodic reaction zone forms enriched in metals is in the accumulation area of tilting grid distributor downstream part.
The base plate of described metal recovery reaction bed bed body is the tilting air distribution plate, and the tilting air distribution plate forms the metallic particles accumulation area of back at tilting grid distributor downstream part of growing up in the recovery metal exit of metal recovery cathodic reaction zone.
The resistivity of described biomass conductive carbon is 0.01～0.5 Ω cm, and specific surface area is 400～900m2/g, and porosity is 0.13 ~ 0.18, and density is 1.5 ~ 2.0.
The utility model adopts the fluidizing medium of the biomass conductive carbon described in the patent application " a kind of preparation method of biomass conductive carbon (200810023948.3) " as spouted fluidized bed electrode, this conduction charcoal has good conductivity (its resistivity only is 0.01～0.5 Ω cm), very bigger serface (400～900m2/g) and porosity (0.13 ~ 0.18), and conduction charcoal density moderate (1.5 ~ 2.0), wide material sources and preparation cost low (only 1000～2000 yuan/ton), be unusual ideal fluidizing medium material, table 1 is a metallic copper, the characteristic of activated carbon and biomass conductive carbon relatively.
The characteristic of table 1 metallic copper, activated carbon and conduction charcoal relatively
| Project | Copper | Activated carbon | Biomass conductive carbon |
| Resistivity, Ω cm | 1.7×10 -6 | 1~10×10 3 | 0.01~5 |
| Specific surface area, m 2/g | 4~8×10 -3 | 500~2000 | 300～500 |
| Density, t/m 3 | ~8.9 | 1.9~2.7 | 2~3 |
| Price unit/ton | 35000～60000 | 300～700 | 200～400 |
Compared with prior art, the utlity model has following advantage:
(1), adopt biomass conductive carbon to replace traditional metallic particles or activated carbon, and have the advantage of metal and activated carbon simultaneously, conductivity is good on the one hand, with its fluid-bed electrode reactor current density height as conducting medium formation; On the other hand, the specific surface area of conduction charcoal is big, has very strong adsorptive power, can it be reduced behind the first adsorbing metal ions again, improves current efficiency greatly, and is especially effective for the metal ion waste water of lower concentration.
(2), the utility model has also adopted double-fluidized-bed electrode technology (comprising purification of waste water fluid-bed electrode and metal recovery fluid-bed electrode), in the purification of waste water fluid-bed electrode with the metal enrichment of lower concentration in biomass conductive carbon, because density metal is much larger than the conduction charcoal, the meeting major sedimentary is sent in the metal recovery fluid-bed electrode by worm conveyor in the bottom that purifies fluid-bed electrode when the metal quality that adsorbs in the biomass conductive carbon acquires a certain degree.In the metal recovery fluid-bed electrode, metal can carry out electrochemical reaction and be dissolved in the solution under the anodic effect, is reduced once more by cathodic reaction, thereby reclaims.With common fluid-bed electrode, after just the metal ion of lower concentration concentrated on the one hand, concentration improved greatly relatively, adopted metallic particles can improve current efficiency greatly as the fluidizing medium of negative electrode, and was beneficial to recycling; On the other hand, in the purification of waste water fluid-bed electrode, by the control of electrode voltage, the metal of the high value that needs are reclaimed has carried out preliminary selectively screening and refining, make that the metal purity in the metal recovery fluid-bed electrode is very high, thereby improve the grade that reclaims metal product.Directly utilize existing metallic particles as negative electrode, reclaim the purity of metal and have only 60～70%, and adopt present technique, the purity that reclaims metal reaches more than 90%.
(3), in addition, the material of the biomass conductive carbon that relates in the utility model is easy to get, low price (200～400 yuan/ton), and hardness is little, little to membranous wearing and tearing, have excellent conducting performance and adsorptive power simultaneously, be the bed material of very ideal fluid-bed electrode.
Description of drawings
Fig. 1 is the utility model biomass conductive carbon double-fluidized-bed electrode reactor structural representation.
Wherein: the 1-waste water pump; 2-waste water header; 3-fluidisation distribution pipe; 4-tilting grid distributor; 5-biomass conductive carbon particle; The 6-osmotic membrane that insulate; The anodic reaction district of 7-purification of waste water; The anode of 8-purification of waste water; 9-purification of waste water positive column egress filtering layer; The outlet of 10-purification of waste water positive column; 11-direct current transmodulator; The cathode feed utmost point of 12-purification of waste water; The cathodic reaction zone of 13-purification of waste water; 14-purification of waste water cathodic area egress filtering layer; The outlet of 15-purification of waste water cathodic area; 16-biomass conductive carbon hopper; Biomass conductive carbon particle after the 17-enriched in metals is in the accumulation area of tilting grid distributor downstream part; The 18-worm conveyor; The anodic reaction district pneumatic outlet of 19-metal recovery reaction bed; 20-biomass conductive carbon circulation feed bin; The 21-worm conveyor; 22-metal recovery anodic reaction district; The 23-reverse checkvalve; The 24-gas blower; 25-wastewater flow by-pass valve control; 26-wastewater flow meter; 27-volume control damper door; The 28-air flowmeter; The 29-reverse checkvalve; 30-fluidisation airduct; 31-air compartment header; 32-tilting air distribution plate; The 33-metallic particles is grown up the back in the accumulation area of tilting grid distributor downstream part; Macrobead collection case after the 34-metal deposition; 35-metal recovery transport trolley; The 36-worm conveyor; 37-metallic particles crushing and screening system; 38-metallic particles hopper; The cathodic reaction zone of 39-metal recovery; The fluidised metallic particles of 40-; 41-regeneration biological matter conduction charcoal particle pooling zone; 42-egress filtering device; The cathodic reaction zone pneumatic outlet of 43-metal recovery reaction bed; The 44-osmotic membrane that insulate; The cathode feed utmost point of 45-metal recovery; The anode feeding electrode of 46-metal recovery; 47-direct current transmodulator; 48-purification of waste water reaction bed; 49-metal recovery reaction bed.
Embodiment
The utility model biomass conductive carbon double-fluidized-bed electrode reactor can be divided into purification of waste water reaction bed 48 and 49 two fluid-bed electrode reaction beds of metal recovery reaction bed, has two places to connect between the two.One be enrichment the biomass conductive carbon of metal from purification of waste water reaction bed 48, export and send in the metal recovery reaction bed 49 by worm conveyor 21; Its two for the biomass conductive carbon after the regeneration by worm conveyor 18 and biomass conductive carbon circulation feed bin 20, from 49 outputs of metal recovery reaction bed and sending in the purification of waste water reaction bed 48.
The main body of purification of waste water reaction bed 48 is fluid-bed electrode reaction beds that adopt the tilting grid distributor, it is characterized in that above tilting grid distributor 4, the angle of inclination of tilting grid distributor 4 is 10～50 °, insulation osmotic membrane 6 is divided into the anodic reaction district 7 of purification of waste water and 13 two zones of cathodic reaction zone of purification of waste water with the space, because the effect of insulation osmotic membrane 6, two interregional liquid and ion can freely exchange, but solid particulate can not exchange.Tilting grid distributor 4 arranged beneath have the fluidisation distribution pipe 3 of waste water header 2, and wastewater flow is regulated by wastewater flow by-pass valve control 25 and wastewater flow meter 26, for preventing return of waste water, between waste water header 2 and wastewater flow meter 26 reverse checkvalve 23 is set.For the fluidized state in 13 two zones of cathodic reaction zone of the anodic reaction district 7 of better control purification of waste water and purification of waste water, waste water header 2 mentioned above, fluidisation distribution pipe 3, wastewater flow by-pass valve control 25, wastewater flow meter 26, reverse checkvalve 29 etc. are provided with respectively below the tilting air distribution plate 4 of two reaction zones.Anode in the purification of waste water reaction bed 48 links to each other with the positive and negative electrode of direct current transmodulator 11 respectively with negative electrode, and voltage is between the two regulated by direct current transmodulator 11.Waste water after the purification is discharged from outlet 10 of purification of waste water positive column and purification of waste water cathodic area outlet 15 respectively.In the anodic reaction district 7 of purification of waste water, insert the anode 8 of one or more purification of waste water that graphite or inert metal (as lead antimony alloy etc.) make, the positive column does not generally need to add fluidized bed material (if desired, yet can add suitable amount of graphite or inert metal particle as fluidized bed material).Insert the negative electrode 12 of one or more purification of waste water in the cathodic reaction zone 13 of purification of waste water, and add an amount of biomass conductive carbon particle 5 (particle diameter is between 1 ~ 5mm) as fluidized bed material.Fluidizing velocities in the cathodic reaction zone 13 of purification of waste water are controlled at 1.4～1.8 times of critical fluidization velocity of biomass conductive carbon particle 5.Biomass conductive carbon is understood the cathode feed utmost point 12 frequent impact with purification of waste water on the one hand in fluid mapper process, thereby is with negative charge, also can capture the metal ion in the waste water on the other hand; Under the effect of electrochemical reaction, the metal ion in the waste water can be reduced into metal simple-substance and be enriched in the biomass conductive carbon or it is surperficial.After biomass conductive carbon pellet density after the enriched in metals is increased to 3～4 times, can assemble in the accumulation area 17 of tilting grid distributor downstream part by the biomass conductive carbon particle after enriched in metals, send in the metal recovery reaction bed 48 by worm conveyor 21.After most of metal in being enriched in the biomass conductive carbon particle is reclaimed by metal recovery reaction bed 49, the density of regeneration biological matter conduction charcoal can be reduced to 1.0 ~ 1.5 times of original biomass conduction charcoal pellet density, because the buoyancy and the rolling action of bubble in the metal recovery reaction bed 49, regeneration biological matter conduction charcoal is carried to solution surface, send by worm conveyor 18, behind biomass conductive carbon circulation feed bin 20 and biomass conductive carbon hopper 16, send into once more in the purification of waste water reaction bed 48.
Metal recovery reaction bed 49 main bodys are three-phase (biomass conductive carbon of air, dilution heat of sulfuric acid, enriched in metals or metallic particles) fluid-bed electrode reaction beds that adopt the tilting air distribution plate, it is characterized in that above tilting air distribution plate 32, the angle of inclination of tilting air distribution plate 32 is 10～50 °, insulation osmotic membrane 44 is divided into metal recovery anodic reaction district 22 and 39 two zones of metal recovery cathodic reaction zone with the space, because the effect of insulation osmotic membrane 44, two interregional liquid and ion can freely exchange, but solid particulate can not exchange.Tilting air distribution plate 32 arranged beneath have the fluidisation airduct 30 of air compartment header 31, and air flow quantity is regulated by volume control damper door 27 and air flowmeter 28, for preventing liquid return, between air compartment header 31 and air flowmeter 28 reverse checkvalve 29 is set.Because the fluidized bed material density variation in metal recovery anodic reaction district 22 and the metal recovery cathodic reaction zone 39 is bigger, air compartment header 31 mentioned above, fluidisation airduct 30, volume control damper door 27, air flowmeter 28, reverse checkvalve 29 etc. all are provided with respectively below the tilting air distribution plate 32 of two reaction zones.Liquid in the metal recovery reaction bed mainly is dilution heat of sulfuric acid (concentration 0.05 ~ 0.2mol/L).Anode in the metal recovery reaction bed 49 links to each other with the positive and negative electrode of direct current transmodulator 47 respectively with negative electrode, and voltage is between the two regulated by direct current transmodulator 47.Fluidizing agent is discharged from the anodic reaction district pneumatic outlet 19 of metal recovery reaction bed and the cathodic reaction zone pneumatic outlet 43 of metal recovery reaction bed respectively.In metal recovery anodic reaction district 22, insert the anode feeding electrode 46 of one or more metal recovery that graphite or inert metal (as lead antimony alloy etc.) make, be fluidized bed material with the biomass conductive carbon particle after the enriched in metals in the positive column, apparent fluidising air velocity is 0.1～0.3m/s.Biomass conductive carbon particle after the enriched in metals on the one hand can with anode feeding electrode 46 frequent impact of metal recovery, obtain positive charge; Under the effect of electrochemical reaction, the metal that is enriched on the biomass conductive carbon can be dissolved into metal ion, and is reduced and reclaims after seeing through insulation osmotic membrane 44 arrival metal recovery cathodic reaction zones 39.Behind the most of dissolving metal in the biomass conductive carbon particle; its density can be reduced to 1.0 ~ 1.5 times of original biomass conduction charcoal pellet density; can be under the buoyancy and rolling action of bubble; float to solution surface; and converge to regeneration biological matter conduction charcoal particle pooling zone 41; send by worm conveyor 18, and, send in the purification of waste water reaction bed 48 by behind biomass conductive carbon circulation feed bin 20 and the biomass conductive carbon hopper 16.In metal recovery cathodic reaction zone 39, the cathode feed utmost point 45 of one or more metal recovery that insertion metal (with intending reclaiming metallographic phase metal together) is made, fluidized bed material is that particle diameter is the metallic particles of 0.1 ~ 0.5mm, and apparent fluidising air velocity is 0.1～0.3m/s.Metallic particles can with the cathode feed utmost point 45 frequent impact of metal recovery; obtain negative charge; under the effect of electrochemical reaction; the metal ion that to come by 44 infiltrations of insulation osmotic membrane from metal recovery anodic reaction district 22 is reduced into metal simple-substance; and be enriched in surface of metal particles, thereby metallic particles can be grown up gradually.When metallic particles is grown up when particle diameter is the particle of 3 ~ 5mm, can be pooled to metallic particles and grow up the back in the accumulation area 33 of tilting grid distributor downstream part, at this moment, send in the macrobead collection case 34 after the metal deposition by worm conveyor, part metal is directly sent to metal recovery transport trolley 35 and is reclaimed, after another part then passes through metallic particles crushing and screening system 37 crushing and screenings, satisfactory metallic particles joins in the metallic particles hopper 38, it is interior as fluidized bed material to send into metal recovery cathodic reaction zone 39 by worm conveyor again, and undesirable metallic particles is sent to metal recovery transport trolley 35 and reclaimed.
Principle of work:
Electro-chemical reaction equations in the negative electrode of purification of waste water reaction bed is as follows:
M
n++n e→M
M is metal or metal ion (1)
Electro-chemical reaction equations in the anode of purification of waste water reaction bed is as follows:
a H
2O-a e+c C
xH
yO
z→a H
++c CO
2+d CO+e H
2O+f O
2
CxHyOz is the organism (2) in the sewage
Electro-chemical reaction equations in the negative electrode of metal recovery reaction bed is as follows:
M
n++n e→
M is metal or metal ion (3)
Electro-chemical reaction equations in the anode of metal recovery reaction bed is as follows:
M-n e→M
n+
M is metal or metal ion (4)
Working process:
Waste water enters the anodic reaction district in the purification of waste water reaction bed, around electrode electrochemical reaction takes place, shown in reaction equation (2).Waste water enters cathodic reaction zone in the purification of waste water reaction bed, impel the biomass conductive carbon particle in the cathodic reaction zone to be in fluidized state, frequent and the cathode feed utmost point collision of fluidised biomass conductive carbon particle, obtain negative charge, biomass conductive carbon utilizes its porous performance trapping metals ion simultaneously, in this process, metal ion generation electrochemical reaction, shown in reaction equation (1), metal ion is reduced into metal simple-substance, and is enriched on the biomass conductive carbon.When the metal of enrichment on the biomass conductive carbon acquired a certain degree, current were difficult to its fluidisation is pooled to the downstream area of tilting grid distributor under action of gravity, send into the metal recovery reaction bed by worm conveyor.
In the anodic reaction district of metal recovery reaction bed, the biomass conductive carbon of enriched in metals is frequent and anode feeding electrode collision under the effect of fluidization air, obtain positive charge, be enriched in the metal generation electrochemical reaction of biomass conductive carbon, shown in reaction equation (4), produce a large amount of metal ions.Behind the dissolving metal of most of enrichment, the density of biomass conductive carbon reduces greatly, can be carried to solution surface by air bubble, and sent back to the cathodic reaction zone of purification of waste water reaction bed by worm conveyor, use as the regenerated biomass conductive carbon.Metal ion sees through the insulation osmotic membrane and enters cathodic reaction zone, in cathodic reaction zone, metallic particles is frequent and cathode feed utmost point collision under the effect of fluidization air, obtain negative charge, electrochemical reaction takes place in metal ion around the metallic particles that has negative charge, shown in the reaction equation (3), the reductive metal simple-substance is enriched in the metallic surface.Make metallic particles grow up gradually.Grow up to a certain degree the time when metallic particles, fluidization air is difficult to its effective fluidisation is pooled to the downstream area of tilting grid distributor under action of gravity, is sent by worm conveyor.The macrobead metal of sending, a part directly reclaims, after another part then passes through metallic particles crushing and screening system, satisfactory metallic particles is added the metal recovery cathodic reaction zone once more as fluidized bed material, the metallic particles that does not meet the particle diameter requirement is reclaimed.
Embodiment 1
The purification of waste water reaction bed cross section of biomass conductive carbon double-fluidized-bed electrode reactor is the square of 0.4m * 0.4m, high 0.6m.Wherein cross section, anodic reaction district is 0.4m * 0.09m, and the cathodic reaction zone cross section is 0.4m * 0.3m, and the insulation osmotic membrane is a glass mat, thick 0.01m, and the inclination angle of tilting grid distributor and horizontal plane is 30 °.The waste water of handling is copper-contained electroplating waste water, and copper ion concentration is 5.3mg/L, and liquid flow rate is 4m
3/ h.Purification of waste water fluid-bed electrode negative and positive two pole tensions are 3V; Cathode feed is three 0.35m * 0.50m fine copper plates of evenly arranging very, and thickness is 5mm; Anode is a slice lead antimony alloy, is of a size of 0.35m * 0.50m, and thickness is 5mm.Adding the biomass conductive carbon grain diameter in the cathodic reaction zone of purification of waste water reaction bed is 2 ~ 3mm, adds quality and is about 2kg.
The metal recovery reaction bed cross section of biomass conductive carbon double-fluidized-bed electrode reactor is the square of 0.1m * 0.1m, high 0.4m.Wherein cross section, anodic reaction district is 0.1m * 0.045m, and the cathodic reaction zone cross section is 0.1m * 0.045m, and the insulation osmotic membrane is a glass mat, thick 0.01m, and the inclination angle of tilting grid distributor and horizontal plane is 30 °.The liquid that adds in the metal recovery reaction bed is the sulphuric acid soln of 0.08mol/L.Metal recovery fluid-bed electrode negative and positive two pole tensions are 6V; Cathode feed is the even 0.1m * 0.35m fine copper plate arranged of a slice very, and thickness is 5mm; The anode feed is a slice lead antimony alloy very, is of a size of 0.35m * 0.50m, and thickness is 5mm.Adding the copper grain diameter in the cathodic reaction zone of metal recovery reaction bed is 0.2 ~ 0.3mm, and the adding total mass is 1.5kg, fluidisation air quantity 12m
3/ h; Biomass conductive carbon quality in the anodic reaction district is about 0.3kg, fluidisation air quantity 6m
3/ h.
Handling the waste water type is copper-contained electroplating waste water, and copper ion concentration is 5.3mg/L, and liquid flow rate is 4m
3/ h.
Implementation result: the copper ion concentration of purifying waste water is 0.03mg/L, and the metal ion rate of recovery reaches 93%, and reclaiming metal purity is 91%.
Embodiment 2
The purification of waste water reaction bed cross section of biomass conductive carbon double-fluidized-bed electrode reactor is the square of 0.4m * 0.4m, high 0.6m.Wherein cross section, anodic reaction district is 0.4m * 0.09m, and the cathodic reaction zone cross section is 0.4m * 0.3m, and the insulation osmotic membrane is a glass mat, thick 0.01m, and the inclination angle of tilting grid distributor and horizontal plane is 30 °.The waste water of handling is copper-contained electroplating waste water, and copper ion concentration is 2.1mg/L, and liquid flow rate is 3.5m
3/ h.Purification of waste water fluid-bed electrode negative and positive two pole tensions are 5V; Cathode feed is three 0.35m * 0.50m fine copper plates of evenly arranging very, and thickness is 5mm; Anode is a slice lead antimony alloy, is of a size of 0.35m * 0.50m, and thickness is 5mm.Adding the biomass conductive carbon grain diameter in the cathodic reaction zone of purification of waste water reaction bed is 2 ~ 3mm, adds quality and is about 3kg.
The metal recovery reaction bed cross section of biomass conductive carbon double-fluidized-bed electrode reactor is the square of 0.1m * 0.1m, high 0.4m.Wherein cross section, anodic reaction district is 0.1m * 0.045m, and the cathodic reaction zone cross section is 0.1m * 0.045m, and the insulation osmotic membrane is a glass mat, thick 0.01m, and the inclination angle of tilting grid distributor and horizontal plane is 30 °.The liquid that adds in the metal recovery reaction bed is the sulphuric acid soln of 0.08mol/L.Metal recovery fluid-bed electrode negative and positive two pole tensions are 8V; Cathode feed is the even 0.1m * 0.35m fine copper plate arranged of a slice very, and thickness is 5mm; The anode feed is a slice lead antimony alloy very, is of a size of 0.35m * 0.50m, and thickness is 5mm.Adding the copper grain diameter in the cathodic reaction zone of metal recovery reaction bed is 0.2 ~ 0.3mm, and the adding total mass is 1.5kg, fluidisation air quantity 12m
3/ h; Biomass conductive carbon quality in the anodic reaction district is about 0.3kg, fluidisation air quantity 5m
3/ h.
Handling the waste water type is copper-contained electroplating waste water, and copper ion concentration is 2.1mg/L, and liquid flow rate is 3.5m
3/ h.
Implementation result: the copper ion concentration of purifying waste water is 0.02mg/L, and the metal ion rate of recovery reaches 96%, and reclaiming metal purity is 94%.
Embodiment 3
The purification of waste water reaction bed cross section of biomass conductive carbon double-fluidized-bed electrode reactor is the square of 0.4m * 0.4m, high 0.6m.Wherein cross section, anodic reaction district is 0.4m * 0.09m, and the cathodic reaction zone cross section is 0.4m * 0.3m, and the insulation osmotic membrane is a glass mat, thick 0.01m, and the inclination angle of tilting grid distributor and horizontal plane is 30 °.The waste water of handling is silver-containing waste water, and concentration of silver ions is 0.9mg/L, and liquid flow rate is 2.5m
3/ h.Purification of waste water fluid-bed electrode negative and positive two pole tensions are 20V; Cathode feed is three 0.35m * 0.50m fine copper plates of evenly arranging very, and thickness is 5mm; Anode is a slice lead antimony alloy, is of a size of 0.35m * 0.50m, and thickness is 5mm.Adding the biomass conductive carbon grain diameter in the cathodic reaction zone of purification of waste water reaction bed is 2 ~ 3mm, adds quality and is about 3kg.
The metal recovery reaction bed cross section of biomass conductive carbon double-fluidized-bed electrode reactor is the square of 0.1m * 0.1m, high 0.4m.Wherein cross section, anodic reaction district is 0.1m * 0.045m, and the cathodic reaction zone cross section is 0.1m * 0.045m, and the insulation osmotic membrane is a glass mat, thick 0.01m, and the inclination angle of tilting grid distributor and horizontal plane is 30 °.The liquid that adds in the metal recovery reaction bed is the sulphuric acid soln of 0.08mol/L.Metal recovery fluid-bed electrode negative and positive two pole tensions are 20V; Cathode feed is the even 0.1m * 0.35m fine copper plate arranged of a slice very, and thickness is 5mm; The anode feed is a slice lead antimony alloy very, is of a size of 0.35m * 0.50m, and thickness is 5mm.Adding silver-plated grain diameter in the cathodic reaction zone of metal recovery reaction bed is 0.2 ~ 0.3mm, and the adding total mass is 2.5kg, fluidisation air quantity 15m
3/ h; Biomass conductive carbon quality in the anodic reaction district is about 0.3kg, fluidisation air quantity 5m
3/ h.
Handling the waste water type is silver-containing waste water, and concentration of silver ions is 0.9mg/L, and liquid flow rate is 2.5m
3/ h.
Implementation result: the concentration of silver ions of purifying waste water is 0.01mg/L, and the metal ion rate of recovery reaches 95%, and reclaiming metal purity is 98%.
Embodiment 4
The purification of waste water reaction bed cross section of biomass conductive carbon double-fluidized-bed electrode reactor is the square of 0.4m * 0.4m, high 0.6m.Wherein cross section, anodic reaction district is 0.4m * 0.09m, and the cathodic reaction zone cross section is 0.4m * 0.3m, and the insulation osmotic membrane is a glass mat, thick 0.01m, and the inclination angle of tilting grid distributor and horizontal plane is 30 °.The waste water of handling is lead waste water, and plumbum ion concentration is 0.6mg/L, and liquid flow rate is 3.0m
3/ h.Purification of waste water fluid-bed electrode negative and positive two pole tensions are 20V; Cathode feed is three 0.35m * 0.50m fine copper plates of evenly arranging very, and thickness is 5mm; Anode is a graphite rod, diameter 0.03m, length 0.50m.Adding the biomass conductive carbon grain diameter in the cathodic reaction zone of purification of waste water reaction bed is 2 ~ 3mm, adds quality and is about 3kg.
The metal recovery reaction bed cross section of biomass conductive carbon double-fluidized-bed electrode reactor is the square of 0.1m * 0.1m, high 0.4m.Wherein cross section, anodic reaction district is 0.1m * 0.045m, and the cathodic reaction zone cross section is 0.1m * 0.045m, and the insulation osmotic membrane is a glass mat, thick 0.01m, and the inclination angle of tilting grid distributor and horizontal plane is 30 °.The liquid that adds in the metal recovery reaction bed is the sulphuric acid soln of 0.08mol/L.Metal recovery fluid-bed electrode negative and positive two pole tensions are 15V; Cathode feed is the even 0.1m * 0.35m fine copper plate arranged of a slice very, and thickness is 5mm; The anode feed is a graphite rod very, diameter 0.03m, length 0.50m.Adding plumbous grain diameter in the cathodic reaction zone of metal recovery reaction bed is 0.2 ~ 0.3mm, and the adding total mass is 4kg, fluidisation air quantity 18m
3/ h; Biomass conductive carbon quality in the anodic reaction district is about 0.3kg, fluidisation air quantity 5m
3/ h.
Handling the waste water type is lead waste water, and plumbum ion concentration is 0.9mg/L, and liquid flow rate is 3.0m
3/ h.
Implementation result: the plumbum ion concentration of purifying waste water is 0.008mg/L, and the metal ion rate of recovery reaches 92%, and reclaiming metal purity is 94%.
Claims (5)
1. biomass conductive carbon double-fluidized-bed electrode reactor of handling low-concentration metallic wastewater, it is characterized in that: comprise purification of waste water reaction bed (48) and metal recovery reaction bed (49), described purification of waste water reaction bed (48) comprises purification reaction bed bed body, waste water header (2), the fluidisation distribution pipe (3) and the first direct current transmodulator (11), be provided with the first insulation osmotic membrane (6) on described purification reaction bed bed body, described purification reaction bed bed body is divided into purification of waste water anodic reaction district (7) and purification of waste water cathodic reaction zone (13) by the described first insulation osmotic membrane (6), in purification of waste water anodic reaction district (7), be provided with anode (8) and purification of waste water positive column outlet (10), in purification of waste water cathodic reaction zone (13), be provided with the cathode feed utmost point (12), biomass conductive carbon particle (5) and purification of waste water cathodic area outlet (15), described anode (8) is connected with the positive pole of the first direct current transmodulator (11), the described cathode feed utmost point (12) is connected with the negative pole of the first direct current transmodulator (11), on described purification reaction bed bed body, also be provided with fluidisation distribution pipe inlet, biomass conductive carbon particle inlet, the outlet of enriched in metals artifact matter conduction charcoal, described fluidisation distribution pipe (3) links with described fluidisation distribution pipe inlet; Described metal recovery reaction bed (49) comprising: metal recovery reaction bed bed body, air compartment header (31), the fluidisation airduct (30) and the second direct current transmodulator (47), be provided with the second insulation osmotic membrane (44) on described metal recovery reaction bed bed body, described metal recovery reaction bed bed body is divided into metal recovery anodic reaction district (22) and metal recovery cathodic reaction zone (39) by the described second insulation osmotic membrane (44), in described metal recovery anodic reaction district (22), be provided with anode feeding electrode (46), anodic reaction district pneumatic outlet, fluidizing medium entered the mouth after biomass conductive carbon reclaimed mouth and enriched in metals, the fluidizing medium inlet is connected with described enriched in metals artifact matter conduction charcoal outlet of drawing together purification of waste water reaction bed (48) after this enriched in metals, described metal recovery cathodic reaction zone (39) is provided with the cathode feed utmost point (44), the outlet of recovery metal, reclaim fluidizing medium inlet and cathodic reaction zone pneumatic outlet, described anode feeding electrode (46) is connected with the positive pole of the second direct current transmodulator (47), the described cathode feed utmost point (44) is connected with the negative pole of the second direct current transmodulator (47), also be provided with the fluidized wind tube inlet on described metal recovery reaction bed bed body, described fluidisation airduct (30) links with described fluidized wind tube inlet.
2. the biomass conductive carbon double-fluidized-bed electrode reactor of processing low-concentration metallic wastewater according to claim 1 is characterized in that: described biomass conductive carbon reclaims mouth and is connected with described biomass conductive carbon particle inlet.
3. the biomass conductive carbon double-fluidized-bed electrode reactor of processing low-concentration metallic wastewater according to claim 1, it is characterized in that: the base plate of described purification reaction bed bed body is tilting grid distributor (4), tilting grid distributor (4) is in purification of waste water cathodic reaction zone (13) bottom, and the biomass conductive carbon after the enriched in metals accumulates in the accumulation area (17) of tilting grid distributor (4) downstream part under action of gravity.
4. the biomass conductive carbon double-fluidized-bed electrode reactor of processing low-concentration metallic wastewater according to claim 1, it is characterized in that: the base plate of described metal recovery reaction bed bed body is tilting air distribution plate (32), and tilting air distribution plate (32) forms the metallic particles accumulation area (33) of back at tilting grid distributor downstream part of growing up in the recovery metal exit of metal recovery cathodic reaction zone (39).
5. the biomass conductive carbon double-fluidized-bed electrode reactor of processing low-concentration metallic wastewater according to claim 1, it is characterized in that: the resistivity of described biomass conductive carbon is 0.01～0.5 Ω cm, specific surface area is 400～900m2/g, porosity is 0.13 ~ 0.18, and density is 1.5 ~ 2.0.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671069B (en) * | 2009-09-23 | 2011-07-06 | 东南大学 | Biomass conductive carbon double-fluidized-bed electrode reactor for treating low-concentration metallic wastewater |
| CN103183400A (en) * | 2011-12-28 | 2013-07-03 | 河南瑞能超微材料股份有限公司 | Novel fluidized bed electrode reactor |
-
2009
- 2009-09-23 CN CN2009202357728U patent/CN201501809U/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671069B (en) * | 2009-09-23 | 2011-07-06 | 东南大学 | Biomass conductive carbon double-fluidized-bed electrode reactor for treating low-concentration metallic wastewater |
| CN103183400A (en) * | 2011-12-28 | 2013-07-03 | 河南瑞能超微材料股份有限公司 | Novel fluidized bed electrode reactor |
| CN103183400B (en) * | 2011-12-28 | 2014-05-14 | 河南瑞能超微材料股份有限公司 | Fluidized bed electrode reactor |
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