CN105884157A - Method for removing and recovering heavy metal in sludge through electrolytic method - Google Patents

Method for removing and recovering heavy metal in sludge through electrolytic method Download PDF

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Publication number
CN105884157A
CN105884157A CN201610377478.5A CN201610377478A CN105884157A CN 105884157 A CN105884157 A CN 105884157A CN 201610377478 A CN201610377478 A CN 201610377478A CN 105884157 A CN105884157 A CN 105884157A
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CN
China
Prior art keywords
sludge
electrolysis
mud
heavy metal
anode region
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Pending
Application number
CN201610377478.5A
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Chinese (zh)
Inventor
胡勤海
裴冬冬
萧晨霞
唐剑昭
徐俊鹏
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Zhejiang University ZJU
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Zhejiang University ZJU
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Priority to CN201610377478.5A priority Critical patent/CN105884157A/en
Publication of CN105884157A publication Critical patent/CN105884157A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/006Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

Abstract

The invention discloses a method for removing and recovering heavy metal in sludge through an electrolytic method. The method includes the steps that the water content of the sludge is adjusted to 90%, then the sludge is stirred; a chemical agent is selectively added, stirred and pretreated; an electrolyzer is assembled and stirs the sludge for electrolysis; the heavy metal is recovered finally. The sludge is directly put in an anode region, the sludge is directly acidized with H+ generated through water electrolysis through an anode, acid does not need to be added additionally, secondary pollution is reduced, and the removal rate of the heavy metal is increased. In addition, the sludge is directly put in the anode region, an electrode can make full contact with the sludge, the current efficiency is fully used, and the electrolysis efficiency is high. The action of electrochemical reaction of a cathode and anode is used well, the membrane exchange area between the sludge and electrolyte is increased, the ionic migration distance is reduced, the heavy metal removal rate is high, the electric energy use ratio is large, the problem of heavy metal recovery is improved, the dual purposes of reducing pollution and recovering resources can be achieved, and environment value and economic benefits are achieved.

Description

A kind of method utilizing electrolysis to remove and reclaim Heavy Metals in Sludge
Technical field
The invention belongs to solid waste resource recovery and utilize field, be specifically related to one and utilize electrolysis The method removed and reclaim Heavy Metals in Sludge.
Background technology
Data shows, municipal sewage plant of China produce mud in Zn content up to 783.4-3096.3mg/kg (dry weight), Cu, up to 131.2-394.5mg/kg (dry weight), additionally contain Having some other heavy metal, such as Cd, Cr, Hg, Ni, Pb etc., the existence of these heavy metals is the tightest Ghost image rings the Subsequent secure of mud to be disposed, and also result in the significant wastage of metals resources.As a example by Zn, By city sludge yield 30,000,000 tons (80% moisture content) in 2010, it is (dry that Zn content presses 1500mg/kg Weight) meter, Zn content the most therein just reaches 9000 tons, offers 15000 in the recent period by Shanghai futures exchange Zn Yuan/ton meter, economic worth reaches 1.35 hundred million yuan.According to China's specific resistance to filtration Market Report (2013 Version) analyze, by 2015, the annual wet mud of urban wastewater treatment firm (moisture content 80%) generation amount To be 33,590,000 tons, i.e. 9.2 ten thousand tons of mud of daily output.If it can thus be seen that not to this part huge sum of money Belong to and be acted upon or recycle, not only drastically influence agricultural sludge compost, burn, landfill etc. follow-up The application of method of disposal, also can cause the great wasting of resources and economic loss.
At present, the disposal to Heavy Metals in Sludge also rests on " innoxious " stage, mainly uses chemistry The leaching of method, bioleaching and electrochemical process etc. realize the removal of Heavy Metals in Sludge.Chemical method mainly passes through Add medicament, change mud Acidity of Aikalinity and metal is carried out dissolution, then precipitate with heavy metal, complexation Realizing the precipitate and separate of heavy metal Deng chemical reaction, but cost is high, technique is loaded down with trivial details, gained precipitate and separate Difficulty, and relatively it is easily generated secondary pollution.Bioleaching is the heavy metal in mud to be turned in acid condition Moving on in liquid phase, then solid-liquid separation obtains the mud of cleaning, is the preferable processing mode of current effect, But the longest, it is generally required to 8-10 days, and process conditions requirement is strict, the existence of heavy metal is also Leaching microorganism can be produced toxic action.Electrochemical process for soil remediation, passes through applied voltage the earliest Make soluble metal ion Migration And Concentration, then removed by means such as electro-deposition or ion exchanges. Owing to electrochemical method is simple to operate, stable, it is not easy to cause the many advantages such as secondary pollution and standby Concerned, but traditional apparatus for electrochemical treatment or garbage is positioned between negative and positive level, at negative electrode Electrolyte is all added, it is impossible to make full use of current efficiency in room and anode chamber;Garbage is positioned over Anode, but electrode is insufficient contact with mud, causes electrolytic efficiency low.Therefore electrochemical treatments is improved Method is that electrochemical process is removed and recycle the waste the key of middle heavy metal.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that one utilizes electrochemical method to remove and returns Receive the new method of Heavy Metals in Sludge.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention step is as follows:
Step one. conditioning of mud moisture content to 90%, stirring;
Take appropriate municipal sewage plant dewatered sludge to be placed in container, add ultra-pure water in calculating ratio, Moisture percentage in sewage sludge is regulated to 90%, and stirs 10 by reinforcement electric blender with 250r/min rotating speed Min, makes mud and water uniformly mix;
Step 2. selectivity adds chelating agen or chelating agent, stirs pretreatment;
In mud after step one processes, selectivity adds chemical agent chelating agen ammonia or chelating agent second Diamidogen, wherein V is compared in the interpolation of analytical pure ammonia volumeAmmonia/VMudIt is 0.12, the volume of analytical pure ethylenediamine Add and compare VEthylenediamine/VMudIt is 0.06.And be slowly stirred with 100r/min rotating speed by reinforcement electric blender 24h, carries out pretreatment.The purpose adding medicament is to utilize complexation or chelation to promote a huge sum of money in mud The removal organic efficiency belonged to, it is possible to without any medicament, be directly entered the 3rd step;
Step 3. assemble electrolysis unit;
With electrodialysis cationic membrane, cathode and anode region is separated, mud pretreated in step 2 is fallen Entering the anode region of electrolysis unit, cathode chamber is the Nacl solution of 0.05mol/L.By agitator and anode Plate is arranged on center, anode region, connects power supply;Nacl solution is 1:2 with the volume ratio of dewatered sludge;
Step 4. stirring electrolysis;
After installing electrolysis unit by step 3, stir with 200r/min rotating speed by reinforcement electric blender, Turning on the power switch, control electric current density is 15mA/Cm2, continuously stirred electrolysis 120h.Electrolysis and Under the effect of stirring, anode region electrolysis water produces H+Carry out acidification sludge, make the soluble heavy metal in mud , in the case of having chelating or chelating agent, there is chelating or complexing, dissolve the huge sum of money in slowly dissolution Belong to ion and arrived cathode chamber by anode region through cationic membrane under the effect of impressed current, and electric with negative electrode The OH that Xie Shui produces+Get off in conjunction with forming precipitation deposition;
Step 5. reclaim Heavy Metals in Sludge;
After electrolysis terminates, filter electrolysis unit cathode chamber solution, obtain heavy metal hydroxide precipitation.Again Different methods is used to reclaim heavy metal according to the kind of heavy metal in precipitation.Nacl after the filtration of cathode chamber Solution reusable edible.
The present invention is had the advantages that
Mud is placed directly in anode region by the present invention, utilizes the H that anode electrolysis water produces+Carry out directly acid Change mud, and need not additionally add acid, decrease secondary pollution, improve the clearance of heavy metal. Additionally, mud is placed directly in anode region, electrode can be fully contacted with mud, makes full use of electric current effect Rate, electrolytic efficiency is high.Make use of the effect of anode and cathode electrochemical reaction simultaneously the most well, increase Film exchange area between mud and electrolyte, decreases ion migration distance, heavy metals removal Rate is high, and utilization rate of electrical is high, the problem improving heavy metal recovery, can reduce pollution and The dual purpose of resource reclaim, has environmental value and economic benefit concurrently.The method can dynamically be followed simultaneously Ring is persistently carried out, and electrolysis time also can carry out reducing or extending according to removal demand, can meet industry Actual demand in production process.
Detailed description of the invention
Below present invention is further described.
Embodiment 1
Step one. conditioning of mud moisture content to 90%, stirring;
Take 2L Hangzhou seven lattice sewage treatment plant dewatered sludge to be placed in container, add ultrapure in calculating ratio Water, regulates moisture percentage in sewage sludge to 90%, and stirs with 250r/min rotating speed by reinforcement electric blender 10min, makes mud and water uniformly mix;
Step 2. assemble electrolysis unit;
Cathode and anode being separated with electrodialysis cationic membrane, the mud after step one being processed pours electrolysis into The anode region of device, cathode chamber loads the Nacl solution of 1L0.05mol/L.By agitator and positive plate It is arranged on center, anode region, connects power supply;
Step 3. stirring electrolysis;
After installing electrolysis unit by step 2, stir with 200r/min rotating speed by reinforcement electric blender Mixing, turn on the power switch, control electric current density is 15mA/Cm2, continuously stirred electrolysis 120h.At electricity Solving and under the effect of stirring, anode region electrolysis water produces H+Carrying out acidification sludge, make in mud is soluble heavy The slow dissolution of metal, and the OH produced with cathodic electrolytic water+Get off in conjunction with forming precipitation deposition;
Step 4. reclaim Heavy Metals in Sludge;
After electrolysis, filter electrolysis unit cathode chamber solution, obtain heavy metal hydroxide precipitation, dry Reclaim.Nacl solution reusable edible after the filtration of cathode chamber.
By this embodiment, zinc Zn in mud after electrolysis, copper Cu, lead Pb content by initial 1888.19mg/kg, 288.55mg/kg and 233.54mg/kg, have decreased to 1102.14mg/kg, 212.29mg/kg and 150.38mg/kg, meets country's relevant emission standards, and clearance is respectively 41.63%, 26.34% and 35.61%.And heavy metal compound precipitation 2.97g is reclaimed on cathode chamber.
Embodiment 2
Step one. conditioning of mud moisture content to 90%, stirring;
Take 2L Hangzhou seven lattice sewage treatment plant dewatered sludge to be placed in container, add ultrapure in calculating ratio Water, regulates moisture percentage in sewage sludge to 90%, and stirs with 250r/min rotating speed by reinforcement electric blender 10min, makes mud and water uniformly mix;
Step 2. 0.12 adds the pure ammonia of complexing agent analysis by volume, stirs pretreatment;
Mud after step one processes presses VAmmonia/VMudIt is the ratio interpolation analytical pure ammonia of 0.12, And it is slowly stirred 24h by reinforcement electric blender with 100r/min rotating speed.
Step 3. assemble electrolysis unit;
With electrodialysis cationic membrane, cathode and anode is separated, then by after in step 2, pretreatment terminates Mud pours the anode region of electrolysis unit into, and cathode chamber loads the Nacl solution of 1L0.05mol/L.To stir Mix device and positive plate is arranged on center, anode region, connect power supply;
Step 4. stirring electrolysis;
After installing electrolysis unit by step 3, stir with 200r/min rotating speed by reinforcement electric blender, Turning on the power switch, control electric current density is 15mA/Cm2, continuously stirred electrolysis 120h.Electrolysis and Under the effect of stirring, anode region electrolysis water produces H+Carry out acidification sludge, make the soluble heavy metal in mud , there is complexing in slowly dissolution in the case of having chelating agent, will a huge sum of money under the effect of impressed current Belong to ion and arrived cathode chamber, and the OH produced with cathodic electrolytic water by anode region through cationic membrane+In conjunction with Form precipitation deposition to get off;
Step 5. reclaim Heavy Metals in Sludge;
After electrolysis, filter electrolysis unit cathode chamber solution, obtain heavy metal hydroxide precipitation, dry back Receive.Nacl solution reusable edible after the filtration of cathode chamber.
By this embodiment, zinc Zn in mud after electrolysis, copper Cu, lead Pb content by initial 1888.19mg/kg, 288.55mg/kg and 233.54mg/kg, have decreased to 528.88mg/kg, 107.74mg/kg and 122.42mg/kg, meets country's relevant emission standards, and clearance is respectively 71.99%, 62.66% and 47.58%.And heavy metal compound precipitation 3.30g is reclaimed on cathode chamber.
Embodiment 3
Step one. conditioning of mud moisture content to 90%, stirring;
Take 2L Hangzhou seven lattice sewage treatment plant dewatered sludge to be placed in container, add ultrapure in calculating ratio Water, regulates moisture percentage in sewage sludge to 90%, and stirs with 250r/min rotating speed by reinforcement electric blender 10min, makes mud and water uniformly mix;
Step 2. 0.06 adds analytical pure ethylenediamine by volume, stirs pretreatment;
Mud after step one processes presses VEthylenediamine/VWater-containing sludgeIt is the ratio interpolation analytical pure second of 0.06 Diamidogen, and it is slowly stirred 24h by reinforcement electric blender with 100r/min rotating speed.
Step 3. assemble electrolysis unit;
With electrodialysis cationic membrane, cathode and anode is separated, by the mud after pretreatment terminates in step 2 Pouring the anode region of electrolysis unit into, cathode chamber loads the Nacl solution of 1L0.05mol/L.By agitator It is arranged on center, anode region with positive plate, connects power supply;
Step 4. stirring electrolysis;
After installing electrolysis unit by step 3, stir with 200r/min rotating speed by reinforcement electric blender Mixing, turn on the power switch, control electric current density is 15mA/Cm2, continuously stirred electrolysis 120h.At electricity Solving and under the effect of stirring, anode region electrolysis water produces H+Carrying out acidification sludge, make in mud is soluble heavy , there is chelation in the slow dissolution of metal in the case of having chelating agen, will under the effect of impressed current Heavy metal ion is arrived cathode chamber, and the OH produced with cathodic electrolytic water by anode region through cationic membrane+ Get off in conjunction with forming precipitation deposition;
Step 5. reclaim Heavy Metals in Sludge;
After electrolysis, filter electrolysis unit cathode chamber solution, obtain heavy metal hydroxide precipitation, dry back Receive.Nacl solution reusable edible after the filtration of cathode chamber.
By this embodiment, zinc Zn in mud after electrolysis, copper Cu, lead Pb content by initial 1888.19mg/kg, 288.55mg/kg and 233.54mg/kg, have decreased to 539.08mg/kg, 140.03mg/kg and 103.90mg/kg, meets country's relevant emission standards, and clearance is respectively 71.45%, 51.47% and 55.51%.And heavy metal compound precipitation 3.31g is reclaimed on cathode chamber.

Claims (3)

1. one kind utilizes the method that electrolysis is removed and reclaimed Heavy Metals in Sludge, it is characterised in that the party Method comprises the following steps:
Step one. conditioning of mud moisture content to 90%, stirring;
Take appropriate municipal sewage plant dewatered sludge to be placed in container, add ultra-pure water in calculating ratio, Moisture percentage in sewage sludge is regulated to 90%, and stirs 10 by reinforcement electric blender with 250r/min rotating speed Min, makes mud and water uniformly mix;
Step 2. assemble electrolysis unit;
With electrodialysis cationic membrane, cathode and anode region is separated, mud pretreated in step one is fallen Entering the anode region of electrolysis unit, cathode chamber is the Nacl solution of 0.05mol/L;By agitator and anode Plate is arranged on center, anode region, connects power supply;Nacl solution is 1:2 with the volume ratio of dewatered sludge;
Step 3. stirring electrolysis;
After installing electrolysis unit by step 2, stir with 200r/min rotating speed by reinforcement electric blender, Turning on the power switch, control electric current density is 15mA/Cm2, continuously stirred electrolysis 120h;It is being electrolysed and is stirring Under the effect mixed, anode region electrolysis water produces H+Carry out acidification sludge, make the soluble heavy metal in mud delay , in the case of having chelating or chelating agent, there is chelating or complexing, dissolve the heavy metal in slow dissolution Ion is arrived cathode chamber, and and catholyte by anode region through cationic membrane under the effect of impressed current The OH that water produces+Get off in conjunction with forming precipitation deposition;
Step 5. reclaim Heavy Metals in Sludge;
After electrolysis terminates, filter electrolysis unit cathode chamber solution, obtain heavy metal hydroxide precipitation;Again Different methods is used to reclaim heavy metal according to the kind of heavy metal in precipitation;Nacl after the filtration of cathode chamber Solution reusable edible.
The most according to claim 1 a kind of utilize electrolysis to remove and reclaim Heavy Metals in Sludge Method, it is characterised in that: in step one, after mud and water uniformly mix, add chemical agent chelating agent Ammonia, V is compared in the interpolation of the purest ammonia volumeAmmonia/VMudIt is 0.12, and by reinforcement electric blender with 100 R/min rotating speed is slowly stirred 24h, carries out pretreatment.
The most according to claim 1 a kind of utilize electrolysis to remove and reclaim Heavy Metals in Sludge Method, it is characterised in that: in step one, after mud and water uniformly mix, add the pure ethylenediamine of chelating agen, V is compared in the volume interpolation of the purest ethylenediamineEthylenediamine/VMudIt is 0.06;And by reinforcement electric blender with 100 R/min rotating speed is slowly stirred 24h, carries out pretreatment.
CN201610377478.5A 2016-05-31 2016-05-31 Method for removing and recovering heavy metal in sludge through electrolytic method Pending CN105884157A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2663161C1 (en) * 2017-08-28 2018-08-01 Федеральное государственное бюджетное образовательное учреждение высшего образования "Вятский государственный университет" (ВятГУ) Method for stabilizing concentration of toxic heavy metal salts in galvanic line recovery bath using electrodialysis
CN109279745A (en) * 2018-09-27 2019-01-29 天津大学 A kind of method that biodegrade chelating agent couples electronic removal desulfurization wastewater sludge heavy-metal
CN111333438A (en) * 2020-03-09 2020-06-26 广州市环境保护工程设计院有限公司 System and method for treating surplus sludge of urban domestic sewage

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2663161C1 (en) * 2017-08-28 2018-08-01 Федеральное государственное бюджетное образовательное учреждение высшего образования "Вятский государственный университет" (ВятГУ) Method for stabilizing concentration of toxic heavy metal salts in galvanic line recovery bath using electrodialysis
CN109279745A (en) * 2018-09-27 2019-01-29 天津大学 A kind of method that biodegrade chelating agent couples electronic removal desulfurization wastewater sludge heavy-metal
CN111333438A (en) * 2020-03-09 2020-06-26 广州市环境保护工程设计院有限公司 System and method for treating surplus sludge of urban domestic sewage

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