CN102381789A - Method for treating smelting wastewater containing heavy metals - Google Patents

Method for treating smelting wastewater containing heavy metals Download PDF

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Publication number
CN102381789A
CN102381789A CN2011102949050A CN201110294905A CN102381789A CN 102381789 A CN102381789 A CN 102381789A CN 2011102949050 A CN2011102949050 A CN 2011102949050A CN 201110294905 A CN201110294905 A CN 201110294905A CN 102381789 A CN102381789 A CN 102381789A
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iron
treatment
wastewater
carbon
electrolysis
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徐晓军
杨津津
黄伟忠
黄昌元
韦建初
王刚
陈晓宏
施国飞
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention discloses a method for treating smelting wastewater containing heavy metals. The method comprises the following steps: 1, the smelting wastewater containing heavy metals is pretreated to remove particulate impurities in the wastewater and adjust the wastewater to be acidic; 2, the wastewater is transferred to an iron-carbon micro-electrolytic reactor to be subjected to single-stage or multi-stage micro-electrolytic electrochemical treatment under acidic conditions to remove most heavy metal ions in the wastewater, the wastewater is adjusted to be weakly alkaline or alkaline, is subjected to single-stage or multi-stage chemical flocculation treatment to further remove other heavy metal ions, and pollutants of arsenic, fluorine, chlorine and the like in the wastewater; and 3, solid-liquid separation is carried out to obtain production water which can be recycled. The method comprises steps of wastewater pretreatment, iron-carbon micro-electrolysis, chemical flocculation and solid-liquid separation which are organically coupled in series. The method which organically combines the micro-electrolysis with the chemical flocculation and allows them to mutually cooperate with each other and co-perform effects has the advantages of simple treating process and technology, low treatment cost, high treatment efficiency, and standard-reached discharge and recovery of the treated wastewater.

Description

A kind of treatment process that contains the heavy metal smelting wastewater
Technical field
The present invention relates to a kind of treatment process that contains the heavy metal smelting wastewater, belong to technical field of environmental science.
Background technology
Contain the heavy metal smelting wastewater and be meant the trade effluent that contains plurality of heavy metal of discharging in the metallurgical industry production process.Containing heavy metal smelting wastewater (like leaded, cadmium, copper, mercury, zinc, arsenic, fluorine etc.) is that environmental pollution the most seriously and to the mankind endangers one of maximum trade effluent.The heavy metal that contains in the heavy metal smelting wastewater generally can not decompose destruction, can only shift its location and change its materialization form.Present in the actual treatment that contains the heavy metal smelting wastewater is used, what mainly adopt is methods such as neutralization precipitation method, ferrite process and sulfuration method, and the quantity of slag is big, meeting produces secondary pollution but neutralization precipitation method and ferrite process exist, and it is higher to vulcanize the method processing cost.And the electrochemical treatment technology is because of having meliority such as high ambient consistency, high energy gamma source utilization ratio, controllability, multifunctionality and economy; Can better realize the purification of waste water and the recovery of heavy metal; Application promise in clinical practice is arranged in heavy metal containing wastewater treatment, and along with the continuous development of this treatment technology makes it become the competitive process for treating heavy-metal waste water that developed recently gets up more widely.
The present invention relates generally to micro-electrolysis method in handling heavy metal-containing waste water, micro-electrolysis method has characteristics such as use range is wide, technology is simple, treatment effect is good, energy consumption is low.The principle of micro-electrolysis method is very simple; Utilize exactly and exist potential difference between the iron carbon granule and formed numerous trickle galvanic cell; And be electrolyte solution with waste water, be main with the electrochemical reaction and multiple effects such as set redox, chemical replacement, handle and contain the heavy metal smelting wastewater.When being immersed in iron carbon granule thing in the waste water, if waste water is acid strong, reduced iron meeting and acid-respons generate Fe 2+, under weak acid or the neutrallty condition because the difference in Electrode Potential between iron and the carbon can form numerous little galvanic cell in the waste water.
When being immersed in iron and carbon in the waste water, if waste water has stronger tart words, reduced iron can with acid-respons generation Fe 2+, under weak acid or the neutrallty condition because the difference in Electrode Potential between iron and the carbon can form numerous little galvanic cell in the waste water.The iron that wherein current potential is low becomes anode, and the carbon that current potential is high becomes negative electrode, and electrochemical reaction takes place, and its reaction process is following:
Anode (Fe): Fe-2e → Fe 2+
Negative electrode (C): 2H ++ 2e → 2 [H] → H 2,
Organic difficult degradation pollutent+ne → easily biodegradable organics,
Heavy metal ion+ne → heavy metal simple substance;
The all right lower heavy metal ion of substitute activity of iron, as:
Fe+Cu 2+→Cu+Fe 2+
If under aerobic existence and the aeration situation, following reaction can also take place in the water:
O 2+4H ++4e→2H 2O,
O 2+2H 2O+4e→4OH
2Fe 2++O 2+4H +→2H 2O+Fe 3+
From reaction, find out; Iron-carbon micro-electrolysis can make heavy metal on negative electrode carbon, separate out; But because the heavy metal ion chemical potential, reach discharging or reuse requirement after the heavy metal ion that adopts single iron-carbon micro-electrolysis to handle to be difficult to make in the waste water is handled, need further to handle.In addition, iron loss H in the reaction +And the OH of micro-electrolysis reaction generation -It is the reason that water outlet pH value raises.And the Fe that produces by iron-carbon micro-electrolysis 2+If, the Fe that the ability oxidation generates 3+, the pH value of raising waste water, Fe 3+Just hydrolysis generates the big Fe (OH) of the polymerization degree gradually 3The colloid throw out can adsorb, condense the heavy metal in the water, nonmetal contaminated ion and other pollutent effectively through self-flocculation, thereby strengthens the decontamination effect improving to waste water.
Combined reactions such as little electrolytic redox, absorption, flocculation, displacement can be removed the metals ion and the impurity of part in the water body preferably, but the pH value only is elevated to 5-6 in the microelectrolysis process, simultaneously Fe 2+The Fe that just oxidation generates under aerobic conditions 3+, do not carry out intensified process, the Fe of generation (OH) 3Colloid throw out amount is few, and a little less than the effect very such as adsorption-flocculation, therefore general little electrolysis need be added subsequent disposal in the back as pre-treatment.Behind iron-carbon micro-electrolysis, adopt the method for chemical flocculation further to handle again, aeration is to improve Fe with the purpose of adding oxygenant in iron-carbon micro-electrolysis and the chemical flocculation process 2+The Fe that oxidation generates 3+Process, also be the process that changes in the waste water such as chemical states such as arsenic, chromium, cadmiums; The purpose that improves the pH value in the water is to make Fe 3+The Fe (OH) that autoflocculation generates 3Isocolloid throw out, the purpose that adds flocculation agent are to promote Fe (OH) 3The production of colloid throw out and tiny flco increase, thereby further improve Fe (OH) 3The effect of the flocculation of colloid throw out, absorption water pollutant; Therefore just can further reduce heavy metal and the content of nonmetal contaminated ion in the waste water well, simultaneously the technological process aeration with add the definite of oxygenant and need confirm according to the character of waste water.
To containing the heavy metal smelting wastewater; The micro-electrolysis method method is good to the heavy metal ion treatment effect; But to nonmetal contaminated ion (like arsenic, fluorine etc.) weak effect; The chemical flocculation method is effective to low-concentration heavy metal ion and nonmetal contaminated ion (like arsenic, fluorine etc.) effect process, but undesirable to higher concentration heavy metal ion treatment effect.The present invention considers micro-electrolysis method and chemical flocculation are combined; The function of two kinds of technology is organically blended; Cooperatively interact and play a role jointly; Give full play to the advantage separately of these two kinds of treatment processs, satisfied and contain characteristics and the requirement that the heavy metal smelting wastewater is handled, solved the method micro-electrolysis method and the independent use of chemical flocculation can not make wastewater treatment problem up to standard; Strengthen containing the removal of pollutent in the heavy metal smelting wastewater simultaneously, thereby realize that efficient, low-cost processes contains the heavy metal smelting wastewater and reclaims the purpose of the heavy metal in the waste water with chemical flocculation.
 
Summary of the invention
The purpose of this invention is to provide a kind of treatment process that contains the heavy metal smelting wastewater; This method is based on the principle of little electrolysis and chemical flocculation; These two kinds of methods organically are coupled to be used for handling contains the heavy metal smelting wastewater, is specially adapted to contain the processing of complicated heavy metal smelting wastewater.
The method removal that the present invention adopts iron-carbon micro-electrolysis and chemical flocculation to handle and combines contains the pollutents such as heavy metal ion in the heavy metal smelting wastewater; Concrete grammar carries out pre-treatment for containing the heavy metal smelting wastewater; Remove granule foreign in the waste water; The adjusting waste water ph is 2.0-5.0, more pretreated waste water is changed in the iron-carbon micro-electrolysis reactor drum, under acidic conditions, carries out after single-stage or multistage little electrolysis electrochemical handle most of heavy metal ion of removing in the waste water; Regulate the pH value; Carry out single-stage or multi-grade chemical flocculation treatment, further remove all the other heavy metal ion and other nonmetal contaminated ions in the waste water, like pollutents such as arsenic, fluorine, chlorine; Carry out solid-liquid separation at last and obtain the production water of recyclable utilization; Entire treatment technology is composed in series by Wastewater Pretreatment, iron-carbon micro-electrolysis, chemical flocculation and solid-liquid separation, and the inventive method can be used separately, also can be to combine to form the technology that complete processing contains the heavy metal smelting wastewater with additive method as a unit process that contains in the processing of heavy metal smelting wastewater.
The pre-treatment that contains the heavy metal smelting wastewater among the present invention is according to the character and the micro-electrolysis reaction requirement that contain the heavy metal smelting wastewater; Before little electrolysis, will contain the heavy metal smelting wastewater earlier and adopt acid or adjusting PH with base to 2 ~ 5; Change wastewater property; Adopt grid, screening, sediment by aeration, precipitate and separate, add in the pretreatment process such as flocculation agent flocculation sediment one or more and remove granule foreign in waste water, the requirement when guaranteeing to contain the heavy metal smelting wastewater and satisfying little electrolysis treatment and guarantee that the iron-carbon micro-electrolysis reaction bed is not stopped up by granule foreign.
The used pH soda acid adjustment of the present invention agent is: (1) alkaline matter is various available industrial alkali wastes, sodium hydroxide, yellow soda ash, Wingdale (powder) or milk of lime (powder); (2) acidic substance are various available industrial waste acids, pending spent acid and acid waste water, sulfuric acid, hydrochloric acid, nitric acid.
Among the present invention the iron-carbon micro-electrolysis reactor drum be with the reaction of iron-carbon micro-electrolysis be master fixed bed, roll bed and fluidized-bed in one or more arbitrary combination; The iron-carbon micro-electrolysis reaction is reaction single-stage or multistage, and every grade of micro-electrolysis reaction residence time is generally 5-120min.
The iron-carbon micro-electrolysis reaction bed is the common mixed bed that constitutes of iron carbon composite grain bed, iron carbon structured packing bed or iron carbon composite grain and structured packing among the present invention; Iron particle and carbon granule total mass sum account for the filler total mass more than 80% in the iron carbon composite grain bed, and the ratio of iron and carbonaceous amount is 1-10:1; Iron carbon structured packing bed is made up of the caked combination with different shapes and micropore iron particle and carbon granule; This combination is that sintering forms (like the structured packing of high-carbon sponge iron); Or be bonded; Wherein the total mass of iron and carbon accounts for the filler total mass more than 80%, and the ratio of iron and carbonaceous amount is 1-10:1; Wherein the iron PM for particulate matter is one or more the arbitrary proportion combination in the ferrous alloy bits PM for particulate matter of cast iron filing, metallic iron, carbon containing metallic iron, carbon containing sponge iron, iron and steel and iron content weight percent >=70%; The carbon granule thing is one or more the arbitrary proportion combination in gac, coke, graphite, thomel, coal, the flyash; One or more elements that also can in little electrolysis composite grain thing and structured packing, add metals such as little copper, aluminium, zinc during electrolysis simultaneously are to strengthen little electrolysis treatment effect, and addition is no more than 10% of total mass.
During the reaction of iron-carbon micro-electrolysis described in the present invention; Can adopt as required continuously or be interrupted aeration mode, add the common use-pattern of oxygenant mode or aeration and interpolation oxygenant and change wastewater property and strengthen little electrolysis treatment effect; The processing of aeration and/or interpolation oxygenant is in the iron-carbon micro-electrolysis reaction process, and/or iron-carbon micro-electrolysis reaction back implements to handle.
Contain the heavy metal smelting wastewater after handling through micro-electrolysis reaction among the present invention; Adjustment pH carries out the chemical flocculation processing behind 6-11; Heavy metal ion and nonmetal contaminated ion pollutents such as (like arsenic, fluorions) in further removal and the reduction waste water, the chemical flocculation treating processes can add flocculation agent enhanced flocculation effect, and the flocculation agent of interpolation is one or more of inorganic flocculating agent and organic floculant; Inorganic flocculating agent is calcium salt, aluminium salt, polyaluminium salts, molysite, polymeric ferric salt; Organic floculant is a polyacrylamide reagent, changes greatly according to waste water quality situation flocculation agent consumption, and the inorganic flocculating agent amount ranges is 0-500 g/m 3Water, organic floculant amount ranges are 0-20g/m 3Water.
The present invention changes wastewater property and strengthens the chemical flocculation impurity-eliminating effect through continuous and discontinuous aeration and/or interpolation oxygenant mode before chemical flocculation is handled or in the process; It generally is single-stage that chemical flocculation is handled, but also can adopt multiple-stage treatment to improve the chemical flocculation impurity-eliminating effect.
Solid-liquid separation is handled the arbitrary combination can adopt one or more methods in settlement separate, filtration, press filtration, the membrane separating method as required among the present invention.
The gas that aeration adopted among the present invention is oxygen, air and oxygen-containing gas, and aeration rate is 0 ~ 3m 3Gas/m 3Water .Min; The oxygenant that adds is ydrogen peroxide 50, superoxide, hypochlorous acid and salt and ozone, and consumption is 0-100g/m 3Water.
The invention has the advantages that: (1) utilization " little electrolytic-chemical flocculation coupled method " is handled and is contained the heavy metal smelting wastewater, and treatment process is simple; As far as containing the heavy metal smelting wastewater; Little electrolysis process is good to the heavy metal ion treatment effect, but to nonmetal contaminated ion (like arsenic, fluorine etc.) weak effect, the chemical flocculation method is effective to low-concentration heavy metal ion and nonmetal contaminated ion (like arsenic, fluorine etc.) effect process; But it is undesirable to higher concentration heavy metal ion treatment effect; Little electrolysis and chemical flocculation organic coupling are combined, remove most heavy metal ion through little electrolysis, for flocculation treatment creates conditions; Strengthen little electrolytic processing efficiency through follow-up flocculation; Bulk treatment is effective, has solved these two kinds of independent uses of method and all can not make wastewater treatment problem up to standard, and water outlet can reach national grade one discharge standard or higher requirement.(2) the single lime neutralisation that more generally adopts, effluent quality is secure, also can obviously reduce sediment weight, and sediment is recyclable after treatment, becomes once more to handle raw material or other raw material.(3) treatment process of the present invention and technology are simple, and processing cost is lower, and processing efficiency is high, and recyclable heavy metal resources can be recycled after processed waste water is up to standard, can reach good comprehensive utilization of resources purpose.
 
Description of drawings
Fig. 1 is the process flow sheet that contains heavy metal smelting wastewater treatment process.
Embodiment
Further specify flesh and blood of the present invention below in conjunction with accompanying drawing, but content of the present invention is not limited to this.
Embodiment 1
Fig. 1 handles for little electrolytic-chemical flocculence and contains heavy metal smelting wastewater art breading schema.Certain large-scale cupric sulfide smeltery production plant heavy metal-containing waste water, waste water is main with production plant ground, smeltery wash-down water, wastewater flow rate 1000t/d; Wastewater pH=5-6 contains heavy metal composition (mg/L) and is: Cu:20.66, Zn:4.53; Pb:1.80, Cd:5.60, As:3.71.In Processing Test, waste water transfers between pH=3.0-3.5 with sulfuric acid after PM for particulate matter is removed in the collecting precipitation pond, changes pretreated waste water over to the fixed bed electrolyzer that declines and carries out iron-carbon micro-electrolysis and handle, and treating processes is carried out aeration; Fixed bed constitutes (structured packing account for filler total mass 30%) by iron and carbon granule filler and the structured packing of iron carbon, and iron carbon mass ratio is 2:1 in structured packing of iron carbon and the iron carbon granule filler, but the structured packing of iron carbon is added with 2% aluminium; The tertiary treatment of even flow iron-carbon micro-electrolysis is adopted in wastewater treatment, and every grade of hydraulic retention is 20min, the 0.8m that adopts aeration rate to be during little electrolysis 3/ m 3Water continuous aeration, little electrolysis finish back waste water and get into the aeration tank and transfer pH=9.0 with sodium hydroxide, continuous aeration 20min again, and aeration rate is 1.5 m 3/ m 3Water makes that most of ferrous ion is converted into ferric ion in the solution, gets into flocculation sedimentation tank then and carries out flocculation sediment and separate; Hydraulic detention time is 30min, water outlet pH=8.5-9.0, and metal content (mg/L) is: Cu:0.084; Zn:0.153, Pb:0.042, Cd:0.0331; As:0.037 has reached the requirement of integrated wastewater discharge standard (GB8978-1966) primary standard, can produce reuse water.
Embodiment 2
Certain cupric sulfide smeltery acid accumulator plant contains heavy metal pickling waste water, wastewater flow rate 200t/d, and waste water sulfur acid 6-8% contains heavy metal composition (mg/L) and is: Cu:181.70, Zn:28.27, Pb:167.05, Cd:15.60, As:176.71, F:319.23.In Processing Test, waste water is transferred about pH=2.5 with lime, staticly settles the back supernatant and changes the electrolyzer (bed rolls) that declines of rolling over to and carry out iron-carbon micro-electrolysis and handle; Iron and carbon granule total mass sum account for filler total mass 100%, and the ratio of iron and carbonaceous amount is 5:1, adopt even flow iron-carbon micro-electrolysis second-stage treatment; Every grade of hydraulic retention is 25min; Little electrolysis finishes back waste water and gets into the aeration flocculation basin, adopts continuous aeration, the 3m that aeration rate is 3/ m 3Water, aeration time 40min transfers pH=11.0 with milk of lime during aeration, adds molecular weight simultaneously and be 800 SEPIGEL 305 20g/ water m 3, adopt the method for press filtration to carry out solid-liquid separation after the aeration flocculation, water outlet metal content (mg/L) is: Cu:0.086; Zn:0.075, Pb:0.12, total Cd:0.0071; Total Cr:0.03, As:0.059, F:1; The heavy metal index is lower than the requirement of integrated wastewater discharge standard (GB8978-1966) primary standard, and waste water is adjusted back pH=8.5-9.0 can directly discharge or produce reuse water.
Embodiment 3
Certain indium zinc smeltery indium zinc production plant factory effluent, wastewater flow rate 50t/d, wastewater pH 2.5-3.0 contains heavy metal composition (mg/L) and is: Cu:4.32, Zn:543.56, Pb:2.77, Cd:5.58, As:5.992, F:19.06.In Processing Test, there is not PM for particulate matter in the waste water, wastewater pH 2.5-3.0 meets the iron-carbon micro-electrolysis processing requirements; Therefore aeration fluidization electrolyzer (aeration fluidized bed) carried out the iron-carbon micro-electrolysis processing bottom waste water directly got into, and iron and carbon granule total mass sum account for filler total mass 100%, and the ratio of iron and carbonaceous amount is 1:1-2:1; Adopt even flow iron-carbon micro-electrolysis one-level to handle; Hydraulic retention is 30min, continuous aeration during little electrolysis, the 3.0m that aeration rate is 3/ m 3Water, most of ferrous ion has been converted into ferric ion in the solution simultaneously.After little electrolysis finished during therefore little electrolysis, with sodium hydroxide+yellow soda ash (ratio 1:1) accent pH=8.5-9.0, add 3# flocculation agent (SEPIGEL 305) consumption again was 10g/ m to waste water at flocculation basin 3Water behind the stirring reaction 10min, adopt pressure filter to carry out solid-liquid separation, but the solid-liquid separation filter residue contains the higher recycling of heavy metal; About solid-liquid separation water outlet pH=8.7, water outlet heavy metal content (mg/L) is: Cu:0.10, Zn:0.093; Pb:0.12, Cd:0.0051, As:0.21; The heavy metal index is lower than the requirement of integrated wastewater discharge standard (GB8978-1966) primary standard, can produce reuse water, and nanofiltration and reverse-osmosis treated are adopted in water outlet again; R-o-water outlet heavy metal content (mg/L) is: pH6-8, Cu≤0.05, Zn≤0.05; Pb≤0.05 Cd≤0.005 As≤0.05 has reached water environment quality standard (GB2828-2002) III generic request, can fully recovering in production.
Embodiment 4: certain medium-sized nickel smeltery mill floor flushing waste water, and wastewater flow rate 500t/d, wastewater pH 6~6.5 contains heavy metal composition (mg/L) and is: Ni: 15.33, Cu:14.21, Co:9.9.In Processing Test, waste water is transferred between pH=3.5-4.0 with sulfur waste acid after 200 mesh are removed granule foreign, changes pretreated waste water over to iron carbon structured packing bed and carries out the iron-carbon micro-electrolysis processing; The iron-carbon micro-electrolysis structured packing is Ф 30 * 20mm; (iron and carbon granule total mass sum account for filler total mass 90% (all the other are impurity) to short column type hollow for Ф 20 * 20mm) high-carbon sponge iron fillers, the inner many micropores of filler; Wherein the carbon granule quality accounts for filler total mass 20%; Adopt the tertiary treatment of even flow iron-carbon micro-electrolysis, every grade of hydraulic retention is 15min, 1 m that adopts aeration rate to be during little electrolysis 3/ m 3Water continuous aeration, little electrolysis finish back waste water entering flocculation basin and transfer pH=8.5-9 with sodium hydroxide, add polyaluminium sulfate 200 g/ m again 3Water and polyacrylamide flocculant 2g/ m 3Water gets into inclined-plate clarifying basin behind the stirring reaction 25min, and the settling tank water outlet is adopted membrane separation process to carry out solid-liquid separation again and handled; Separating water outlet is about pH=8.5, and heavy metal content (mg/L) is: Ni:0.0053, Cu:0.054; Co:0.0031, heavy metal content have reached water environment quality standard (GB2828-2002) III generic request, but fully recovering is in producing; Little electrolysis and flocculation basin sediment metal content are higher, return smelting system and carry out recycling.
Embodiment 5
Certain lead-zinc smelting smeltery acid accumulator plant pickling waste waters, wastewater flow rate 150m3/h, waste water sulfur acid 4-6%, metal ingredient (mg/L) is: Zn:145.80, Pb:94.81, Cu:3.96, Cd:14.60, As:376.71.In Processing Test, waste water is transferred pH=2.5-3.0 with limestone powder, and clear liquid waste water carries out the iron-carbon micro-electrolysis processing after the waste water press filtration, adopts the tertiary treatment of even flow iron-carbon micro-electrolysis aeration, the 0.8m3/ m3 water that aeration rate is.First with secondary be iron (cast iron filing) and carbon granule mixed bed; Cast iron filing and activated carbon particle total mass sum account for filler total mass 100%; The ratio of iron and carbonaceous amount is 2:1, and every grade of hydraulic retention is 15min, and the third stage is that iron-carbon micro-electrolysis is handled employing iron carbon structured packing bed; Structured packing is identical with embodiment 4, and hydraulic retention is 20min.Little electrolysis finishes waste water entering aeration tank, back and transfers pH=8.5-9.0 with milk of lime, adds ydrogen peroxide 50 10 g/m again 3Water, 1 m that continuous aeration 10min, aeration rate are 3/ m 3Water makes that ferrous ion is converted into ferric ion in the solution, and trivalent arsenic is converted into the arsenic of pentavalent, gets into flocculation basin then, adds SEPIGEL 305 2g/ m again 3Water behind the stirring reaction 15min, adopts settlement separate method to carry out solid-liquid separation; After the solid-liquid separation in the water outlet metal content (mg/L) be: Zn:0.075, Pb:0.093, Cu:0.092; Cd:0.0091; As:0.079, the heavy metal index is lower than the requirement of integrated wastewater discharge standard (GB8978-1966) primary standard, can produce reuse water; Little electrolysis and flocculation basin sediment metal content are higher, return smelting system and carry out recycling.Nanofiltration and reverse-osmosis treated are adopted in the water outlet of little electrolysis-flocculation treatment again, and r-o-water outlet heavy metal content is lower than water environment quality standard (GB2828-2002) III class standard, can fully recovering in production.

Claims (14)

1. a treatment process that contains the heavy metal smelting wastewater is characterized in that comprising the steps:
The smelting wastewater that (1) will contain heavy metal carries out pre-treatment, removes granule foreign in the waste water, and the adjusting waste water ph is 2.0-5.0;
(2) pretreated waste water is changed in the iron-carbon micro-electrolysis reactor drum, under acidic conditions, carry out the reaction of single-stage or multistage iron-carbon micro-electrolysis, every grade of micro-electrolysis reaction residence time is 5-120min, removes the most heavy metal ion in the waste water;
(3) with the waste water after step (2) processing, after adjusting pH value is 6-11, adds as required or do not add flocculation agent and carry out single-stage or multi-grade chemical flocculation treatment, wherein adding the inorganic flocculating agent amount ranges is 0-500 g/m 3, the organic floculant amount ranges is 0-20g/m 3
(4) step (3) processed waste water is carried out solid-liquid separation, detect back up to standard discharging and/or recycling as water of productive use.
2. according to the treatment process of stating of claim 1, it is characterized in that: adopt grid, screening, sediment by aeration, precipitate and separate, add in the pretreatment process such as flocculation agent flocculation sediment one or more and remove granule foreign in waste water.
3. according to the said treatment process of claim 1, it is characterized in that: the iron-carbon micro-electrolysis reactor drum be with the iron-carbon micro-electrolysis reaction be master's fixed bed, one or more arbitrary combination in roll bed and the fluidized-bed.
4. according to claim 1 and 3 said treatment processs; It is characterized in that: the iron-carbon micro-electrolysis reaction bed is iron carbon composite grain bed and/or iron carbon structured packing bed; Wherein iron particle and carbon granule total mass sum account for the filler total mass more than 80% in the iron carbon composite grain bed, and the ratio of iron and carbonaceous amount is 1-10:1; The total mass of iron and carbon accounts for the filler total mass more than 80% in the iron carbon structured packing bed, and the ratio of iron and carbonaceous amount is 1-10:1.
5. according to claim 1 and 4 said treatment processs, it is characterized in that: in little electrolysis composite grain and structured packing, can add one or more elements in little copper, aluminium, the zinc metal, addition is no more than 10% of total mass.
6. according to claim 1 and 4 said treatment processs, it is characterized in that: the iron PM for particulate matter is one or more the arbitrary proportion combination in the ferrous alloy bits PM for particulate matter of cast iron filing, metallic iron, carbon containing metallic iron, carbon containing sponge iron, iron and steel and iron content weight percent >=70%; The carbon granule thing is one or more the arbitrary proportion combination in gac, coke, graphite, thomel, coal, the flyash.
7. treatment process according to claim 1 is characterized in that: in the iron-carbon micro-electrolysis reaction process, use continuous aeration or be interrupted the aeration processing and/or the interpolation oxidizer treatment, strengthen little electrolysis and remove heavy metal ion.
8. treatment process according to claim 7 is characterized in that: the processing of aeration and/or interpolation oxygenant is in the iron-carbon micro-electrolysis reaction process, and/or iron-carbon micro-electrolysis reaction back implements to handle.
9. treatment process according to claim 1 is characterized in that: add flocculation agent in the chemical flocculation treating processes, flocculation agent is one or more of inorganic flocculating agent and organic floculant.
10. treatment process according to claim 9 is characterized in that: inorganic flocculating agent is calcium salt, aluminium salt, polyaluminium salts, molysite, polymeric ferric salt, and organic floculant is the polyacrylamide medicament.
11. treatment process according to claim 1 is characterized in that: before chemical flocculation is handled or in the process waste water is carried out aeration and/or add oxygenant and carry out oxide treatment change wastewater property.
12. want 8 or 11 described treatment processs according to right, it is characterized in that: gases used oxygen, air and the oxygen-containing gas of can be of aeration when aeration is handled, aeration rate is 0 ~ 3m 3/ m 3Water .Min; The oxygenant that adds is ydrogen peroxide 50, superoxide, hypochlorous acid and salt, ozone, and consumption is 0-100g/m 3Water.
13. according to the said treatment process of claim 1, it is characterized in that: the solid-liquid separation treatment process is one or more arbitrary combination in settlement separate, filtration, press filtration, the membrane separating method.
14., it is characterized in that using separately or using as a processing unit in the wastewater treatment process based on the described processing method of claim 1.
CN2011102949050A 2011-10-08 2011-10-08 Method for treating smelting wastewater containing heavy metals Pending CN102381789A (en)

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Cited By (28)

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CN102897956A (en) * 2012-10-29 2013-01-30 云南锡业集团有限责任公司研究设计院 Method for treating high-arsenious wastewater
CN102923891A (en) * 2012-11-12 2013-02-13 清远市灵捷制造化工有限公司 Microelectrolysis combined process used for waste water treatment
CN102976532A (en) * 2012-12-28 2013-03-20 湘潭大学 Method for treating fluorine-containing polymetallic acidic smelting wastewater by internal electrolysis and coprecipitation of ferric-carbon
CN103172143A (en) * 2013-03-21 2013-06-26 东阳市清源环保科技有限公司 Method for recycling copper from D-threo-beta-Methylsulfonylphenylserine ethyl ester production wastewater
CN103241796A (en) * 2013-05-31 2013-08-14 邓杰帆 Process and device for performing continuous filtration and adsorption treatment on sewage by using graphene
CN103359813A (en) * 2013-08-09 2013-10-23 中国矿业大学(北京) Water sterilizing system
CN103466847A (en) * 2013-08-25 2013-12-25 云南锡业集团有限责任公司研究设计院 Method for efficiently, simply and conveniently treating tin smelting low arsenic wastewater
CN103708679A (en) * 2013-12-26 2014-04-09 浙江工商大学 Treatment process for fluorine chemical wastewater
CN104192869A (en) * 2014-08-25 2014-12-10 湖南江冶机电科技股份有限公司 Purification method and device of desulfurization lead plaster filtrate
CN104743643A (en) * 2015-03-30 2015-07-01 湖州华鼎贸易有限公司 Novel compound flocculant and application thereof
CN104944649A (en) * 2015-07-10 2015-09-30 常州市龙润机械有限公司 Chemical waste water treatment method and treatment device
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CN105236522A (en) * 2015-11-11 2016-01-13 南京格洛特环境工程股份有限公司 Novel heavy metal wastewater preprocessing reactor and application
CN105600982A (en) * 2015-12-24 2016-05-25 南京格洛特环境工程股份有限公司 Process for treating polluted acid water in copper smelting by utilizing calcium and magnesium desulfurization sludge
CN105601013A (en) * 2015-12-24 2016-05-25 南京格洛特环境工程股份有限公司 Zero emission and recycling co-treatment method for copper smelting dirty acid water and magnesium desulfurization sludge
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CN107324530A (en) * 2017-06-29 2017-11-07 苏州科博思设备工程有限公司 A kind of sewage water treatment method
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CN107954549A (en) * 2017-12-04 2018-04-24 天津科技大学 A kind of absorption-aeration-nanofiltration group technology and its special purpose device for arsenic-containing water processing
CN109279730A (en) * 2018-12-05 2019-01-29 浙江海洋大学 A kind of technique handling copper smelting heavy metal in waste water
CN110171892A (en) * 2019-06-21 2019-08-27 湖南瀚洋环保科技有限公司 A kind of processing method of the chrome plating waste liquor containing cyanogen
CN110590027A (en) * 2019-09-04 2019-12-20 山西晋城无烟煤矿业集团有限责任公司 Defluorination method for industrial sewage
CN111282317A (en) * 2020-03-11 2020-06-16 吕文广 Method for removing solid particles in nickel-cobalt-manganese lithium salt and lithium battery material
CN111392959A (en) * 2020-03-04 2020-07-10 重庆立克微生态科技有限公司 Heavy metal wastewater purification treatment system and application thereof

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CN102826704B (en) * 2012-09-20 2015-04-08 江苏艾特克环境工程有限公司 Recycle system for recycled water
CN102897956A (en) * 2012-10-29 2013-01-30 云南锡业集团有限责任公司研究设计院 Method for treating high-arsenious wastewater
CN102923891A (en) * 2012-11-12 2013-02-13 清远市灵捷制造化工有限公司 Microelectrolysis combined process used for waste water treatment
CN102976532A (en) * 2012-12-28 2013-03-20 湘潭大学 Method for treating fluorine-containing polymetallic acidic smelting wastewater by internal electrolysis and coprecipitation of ferric-carbon
CN103172143A (en) * 2013-03-21 2013-06-26 东阳市清源环保科技有限公司 Method for recycling copper from D-threo-beta-Methylsulfonylphenylserine ethyl ester production wastewater
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CN103466847A (en) * 2013-08-25 2013-12-25 云南锡业集团有限责任公司研究设计院 Method for efficiently, simply and conveniently treating tin smelting low arsenic wastewater
CN103708679A (en) * 2013-12-26 2014-04-09 浙江工商大学 Treatment process for fluorine chemical wastewater
CN104192869A (en) * 2014-08-25 2014-12-10 湖南江冶机电科技股份有限公司 Purification method and device of desulfurization lead plaster filtrate
CN104743643A (en) * 2015-03-30 2015-07-01 湖州华鼎贸易有限公司 Novel compound flocculant and application thereof
CN104944649A (en) * 2015-07-10 2015-09-30 常州市龙润机械有限公司 Chemical waste water treatment method and treatment device
CN105152424A (en) * 2015-10-19 2015-12-16 无锡清杨机械制造有限公司 Device for removing heavy metal ions in industrial wastewater
CN105236522A (en) * 2015-11-11 2016-01-13 南京格洛特环境工程股份有限公司 Novel heavy metal wastewater preprocessing reactor and application
CN105600982B (en) * 2015-12-24 2018-05-18 南京格洛特环境工程股份有限公司 A kind of technique using calcium, magnesium processes desulfurization sludge processing Copper making waste acid water
CN105601013A (en) * 2015-12-24 2016-05-25 南京格洛特环境工程股份有限公司 Zero emission and recycling co-treatment method for copper smelting dirty acid water and magnesium desulfurization sludge
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CN105776683A (en) * 2016-05-11 2016-07-20 常熟林润氟硅材料有限公司 High-frequency pulse electrochemical wastewater treatment system
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CN106746172A (en) * 2016-11-17 2017-05-31 贵州省植物园 A kind of livestock and poultry leachate processing method of content of beary metal high
CN107324530A (en) * 2017-06-29 2017-11-07 苏州科博思设备工程有限公司 A kind of sewage water treatment method
CN107324531A (en) * 2017-06-29 2017-11-07 苏州科博思设备工程有限公司 A kind of sewage disposal device
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Application publication date: 20120321