CN104445732A - Process for removing thallium from thallium-containing heavy metal wastewater through neutralization and flocculation - Google Patents

Process for removing thallium from thallium-containing heavy metal wastewater through neutralization and flocculation Download PDF

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Publication number
CN104445732A
CN104445732A CN201410685459.XA CN201410685459A CN104445732A CN 104445732 A CN104445732 A CN 104445732A CN 201410685459 A CN201410685459 A CN 201410685459A CN 104445732 A CN104445732 A CN 104445732A
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China
Prior art keywords
thallium
heavy metal
reaction tank
coagulation
metal wastewater
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Pending
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CN201410685459.XA
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Chinese (zh)
Inventor
李迪汉
彭黎胜
张天芳
伏东才
林文军
熊智
姜晴
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Zhuzhou Smelter Group Co Ltd
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Zhuzhou Smelter Group Co Ltd
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Priority to CN201410685459.XA priority Critical patent/CN104445732A/en
Publication of CN104445732A publication Critical patent/CN104445732A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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 process for removing thallium from thallium-containing heavy metal wastewater through neutralization and flocculation. The process comprises the following steps: performing primary treatment, namely adjusting the pH value of thallium-containing heavy metal wastewater to be more than 7through acid and alkali, adding an efficient coagulant, sulfide and a flocculant, and performing solid-liquid separation through a slanting board sedimentation pool; performing secondary treatment, namely adding sulfide, diatomite and the flocculant into supernatant purified water after primary treatment, and performing solid-liquid separation through the slanting board sedimentation pool; adjusting the purified water subjected to secondary treatment to be neutral, adding iron salt, and finally filtering through a filter and directly discharging to the outside. Due to the adoption of the technical scheme, the removal rate of thallium and other heavy metal ions in the heavy metal wastewater can be effectively increased, the environmental pollution can be avoided, and the medicament cost can be reduced.

Description

One contains in thallium heavy metal wastewater thereby and coagulation process for removing thallium
Technical field
The present invention relates to a kind of containing thallium process for treating heavy-metal waste water, what particularly relate to the process generations such as a kind of coloured industry mining, ore dressing, smelting, processing contains one or more heavy metal waste water treatment process such as cadmium, arsenic, lead, zinc, copper, thallium.
Background technology
Industrialized developing rapidly makes a large amount of heavy metal wastewater therebies be discharged in environment, acid heavy metal wastewater pH lower (pH value is between 4-6), and containing contents of many kinds of heavy metal ion, as Cu 2+, Cd 2+, Pb 2+, Zn 2+, Hg 2+, Tl +, Tl 2+deng, they cannot be decomposed by organism, once will constantly accumulate in the environment after entered environment, will produce severe contamination to water body, even destroy ecotope.
Thallium (Tl) belongs to eare scattered metals, and be the heavy metal contaminants of severe toxicity, thallium poisoning can cause respiratory system, Digestive tract illness, finally causes nervous system damage, and serious thallium poisoning is enough to cause death.
From the 60's of last century, potassium permanganate starts to be applied to waste water containing thallium processing technology field, domesticly at the beginning of the 80's of 20th century, carries out systematic study to potassium permanganate depollution technology.Potassium permanganate has strong oxidizing property, can by T1 +be oxidized to T1 3+, Tl sedimentation is removed by recycling alkaline condition.In addition, the newly created MnO2 generated after potassium permanganate reaction has higher adsorptive power to metallic cation, and this ability mainly comes from its surface chemical property.Hydrated manganese dioxide has the specific surface area far above solid manganese dioxide, and its surface is containing abundant hydroxyl, therefore has higher reactive behavior and more activated adsorption current potential.This method is applicable to the waste water containing thallium process such as river, but undesirable to the removal effect of thallium in lead-zinc smelting heavy metal wastewater thereby, and cost is higher.
Electrochemical process heavy metal containing wastewater treatment technology mainly adds a set of electrochemical treatment system in flocculation conventional at present, precipitation waste water treatment process, reduces heavy metal content in water outlet further.By the principle such as electrochemistry, aeration by thallium and heavy metal combined removal.But project investment is higher, cost is higher, and is not suitable for high density waste water containing thallium.
Iron carbon catalysis and micro-electrolysis technology is in cold situation, utilizes the micro-electrolysis stuffing of filling in light electrolysis equipment to produce " galvanic cell " effect, processes under the effect of katalaze enzyme to waste water.When after water flowing, can be formed in equipment " galvanic cell " that countless potential differences reaches 1.2V or 1.5V." galvanic cell " does ionogen with waste water, forms electric current carry out electrolytic oxidation and reduction treatment to waste water, to reach the object of removal heavy metal and degradable organic pollutant by electric discharge.This method processed waste water colourity is higher, and is not suitable for high density waste water containing thallium.
Summary of the invention
The invention provides a kind of clean and effective, the one that simple to operate, preventing from heavy metal impact load ability is strong containing in thallium heavy metal wastewater thereby and coagulation process for removing thallium, its concrete technology comprises:
One contains in thallium heavy metal wastewater thereby and coagulation process for removing thallium, and to contain thallium heavy metal wastewater thereby for handling object, by waste water second-stage treatment, guarantee thallium and heavy metal element qualified discharge, its concrete technology comprises:
A. coagulation: to extremely alkaline by acid-alkali accommodation containing thallium heavy metal wastewater thereby, add coagulant, sulfide, flocculation agent successively, carry out solid-liquid separation finally by inclined plate sedimentation pond I, remove most of thallium and heavy metal ion.
B. second-stage treatment: the supernatant after coagulation solid-liquid separation adds sulfide, diatomite, flocculation agent in purifying waste water successively, carries out solid-liquid separation by inclined plate sedimentation pond II, and the degree of depth removes thallium wherein and heavy metal ion.
C. again acid-alkali accommodation is carried out to purifying waste water after second-stage treatment, after being adjusted to neutrality, add molysite, direct outer row after eventually passing frit.
Further, coagulation in described steps A is undertaken by four reaction tanks, inclined plate sedimentation pond and sludge sump, the first reaction tank, the second reaction tank, the 3rd reaction tank, the 4th reaction tank is flow through successively containing thallium heavy metal wastewater thereby, neutralizing agent is added in the first reaction tank, described neutralizing agent is one or more in milk of lime, sodium hydroxide or Wingdale, regulates pH to 9-11; In the second reaction tank, add coagulant, described coagulant is one or more in Tai-Ace S 150, polymerize aluminum chloride, polyaluminium sulfate; In the 3rd reaction tank, add sulfide, described sulfide is one or more in sodium sulphite, sulfuration ammonia, potassium sulphide, Iron sulfuret; In the 4th reaction tank, add flocculation agent, described flocculation agent is one or more in polyacrylamide, sodium polyacrylate; Carry out solid-liquid separation finally by inclined plate sedimentation pond I, supernatant is purified waste water and is entered second-stage treatment operation, and mud enters sludge sump and processes.
Further, second-stage treatment in described step B is undertaken by three reaction tanks and inclined plate sedimentation pond II, supernatant after coagulation solid-liquid separation is purified waste water and the supernatant liquor of sludge sump flows through the 5th reaction tank successively, 6th reaction tank, 7th reaction tank, the sulfide added in the 5th reaction tank, described sulfide is sodium sulphite, sulfuration ammonia, potassium sulphide, one or more in Iron sulfuret, diatomite is added in the 6th reaction tank, flocculation agent is added in the 7th reaction tank, described flocculation agent is polyacrylamide, one or more in sodium polyacrylate, solid-liquid separation is carried out finally by inclined plate sedimentation pond II, the degree of depth removes thallium wherein and heavy metal ion.
Further, in described step C, second-stage treatment after purification water, by adding sulfuric acid, regulates pH to 6-9, then add molysite, described molysite is one or more in ferrous sulfate, ferric sulfate, bodied ferric sulfate, poly-ferric chloride, ferric sulfate of polymerized silica, PPFS.
Further, in described step C, the filled media in strainer is one or more in activated carbon, zeolite, diatomite, manganese sand.
The invention has the advantages that: by waste water secondary except thallium, ensure that the degree of depth of waste water thallium is removed, ICP-MS instrument (the VG PQ3ICP-MS that power & light company of the U.S. produces) is used to measure, influent density be 0.000005-0.00007g/L containing thallium concentration≤0.0000001g/L after thallium heavy metal containing wastewater treatment, can stablize and reach " water environment quality standard " (GB3838-2002) limit value.
The present invention can remove the heavy metals such as Cu in waste water, cadmium, lead, zinc while thallium in stable removing heavy metals waste water, realizes the deep purifying of thallium and various heavy in waste water, has good application prospect.
Accompanying drawing explanation
Fig. 1 is the processing technological flow figure containing thallium heavy metal wastewater thereby of the present invention.
Embodiment
One contains in thallium heavy metal wastewater thereby and coagulation process for removing thallium, it is characterized in that, to contain thallium heavy metal wastewater thereby for handling object, by waste water second-stage treatment, guarantees thallium and heavy metal element qualified discharge.Its concrete technology comprises:
1) coagulation part comprises: to containing thallium heavy metal wastewater thereby by one or more in the first reaction tank feeding lime breast, sodium hydroxide or Wingdale, regulating pH to 9-11, making Tl 3+with OH -form the Tl(OH of indissoluble) 3, OH -precipitation of hydroxide is formed in the basic conditions with most of heavy metal ion; In the second reaction tank, add one or more efficient flocculants in Tai-Ace S 150, polymerize aluminum chloride, polyaluminium sulfate, impel precipitation of hydroxide to form larger alumen ustum; Add one or more in sodium sulphite, sulfuration ammonia, potassium sulphide, Iron sulfuret at the 3rd reaction tank, make Tl +with S 2-form the Tl of indissoluble 2s, Tl 3+with S 2-form the T1 of indissoluble 2s 3, S 2-sulfide precipitation is formed with part heavy metal ion; One or more in polyacrylamide, sodium polyacrylate are added at the 4th reaction tank, form larger alumen ustum be beneficial to sedimentation by adsorbing de-steady, bridging and sweep coagulation effect, carry out solid-liquid separation finally by inclined plate sedimentation pond I, remove most of thallium and heavy metal ion.Supernatant after solid-liquid separation is purified waste water and is entered second-stage treatment operation, and mud enters sludge sump and processes.
2) second-stage treatment part comprises: purify waste water and sludge sump supernatant liquor to one-level supernatant, adds one or more in sodium sulphite, sulfuration ammonia, potassium sulphide, Iron sulfuret by the 5th reaction tank, one-level supernatant is purified waste water and Tl residual in sludge sump supernatant +with S 2-form the Tl of indissoluble 2s, Tl 3+with S 2-form the T1 of indissoluble 2s 3, S 2-sulfide precipitation is formed with part heavy metal ion, diatomite is added again by the 6th reaction tank, throw out in the specific surface area planar water utilizing it larger reaches the object of co-precipitation, flocculation agent is added again by the 7th reaction tank, described flocculation agent is one or more in polyacrylamide, sodium polyacrylate, carry out solid-liquid separation finally by inclined plate sedimentation pond II, the degree of depth removes thallium wherein and heavy metal ion.
3) sulphur acid for adjusting pH is added again to 6-9 to purifying waste water after second-stage treatment, add one or more in ferrous sulfate, ferric sulfate, bodied ferric sulfate, poly-ferric chloride, ferric sulfate of polymerized silica, PPFS, remove S unnecessary in purifying waste water 2-, be the metre filter of one or more in activated carbon, zeolite, diatomite, manganese sand finally by filled media, direct outer row after removing remaining throw out; Back washing strength is 12 L/m 2.S, when strainer pressure at two ends is more than 0.15Mpa, back flushing need be carried out to strainer.

Claims (5)

1. contain in thallium heavy metal wastewater thereby and a coagulation process for removing thallium, it is characterized in that: to contain thallium heavy metal wastewater thereby for handling object, by waste water second-stage treatment, guarantee thallium and heavy metal element qualified discharge, its concrete technology comprises:
A. coagulation comprises: to extremely alkaline by acid-alkali accommodation containing thallium heavy metal wastewater thereby, add coagulant, sulfide, flocculation agent successively, carry out solid-liquid separation, remove most of thallium and heavy metal ion finally by inclined plate sedimentation pond I;
B. second-stage treatment comprises: the supernatant after coagulation solid-liquid separation adds sulfide, diatomite, flocculation agent in purifying waste water successively, carries out solid-liquid separation by inclined plate sedimentation pond II, and the degree of depth removes thallium wherein and heavy metal ion;
C. again acid-alkali accommodation is carried out to purifying waste water after second-stage treatment, after being adjusted to neutrality, add molysite, direct outer row after eventually passing frit.
2. one as claimed in claim 1 contains in thallium heavy metal wastewater thereby and coagulation process for removing thallium, it is characterized in that: the coagulation in described steps A is undertaken by four reaction tanks, inclined plate sedimentation pond and sludge sump, the first reaction tank, the second reaction tank, the 3rd reaction tank, the 4th reaction tank is flow through successively containing thallium heavy metal wastewater thereby, neutralizing agent is added in the first reaction tank, described neutralizing agent is one or more in milk of lime, sodium hydroxide or Wingdale, regulates pH to 9-11; In the second reaction tank, add coagulant, described coagulant is one or more in Tai-Ace S 150, polymerize aluminum chloride, polyaluminium sulfate; In the 3rd reaction tank, add sulfide, described sulfide is one or more in sodium sulphite, sulfuration ammonia, potassium sulphide, Iron sulfuret; In the 4th reaction tank, add flocculation agent, described flocculation agent is one or more in polyacrylamide, sodium polyacrylate; Carry out solid-liquid separation finally by inclined plate sedimentation pond I, supernatant is purified waste water and is entered second-stage treatment operation, and mud enters sludge sump and processes.
3. one as claimed in claim 1 contains in thallium heavy metal wastewater thereby and coagulation process for removing thallium, it is characterized in that: the second-stage treatment in described step B is undertaken by three reaction tanks and inclined plate sedimentation pond II, supernatant after coagulation solid-liquid separation is purified waste water and the supernatant liquor of sludge sump flows through the 5th reaction tank successively, 6th reaction tank, 7th reaction tank, the sulfide added in the 5th reaction tank, described sulfide is sodium sulphite, sulfuration ammonia, potassium sulphide, one or more in Iron sulfuret, diatomite is added in the 6th reaction tank, flocculation agent is added in the 7th reaction tank, described flocculation agent is polyacrylamide, one or more in sodium polyacrylate, solid-liquid separation is carried out finally by inclined plate sedimentation pond II, the degree of depth removes thallium wherein and heavy metal ion.
4. one as claimed in claim 1 contains in thallium heavy metal wastewater thereby and coagulation process for removing thallium, it is characterized in that: in described step C, second-stage treatment after purification water is by adding sulfuric acid, regulate pH to 6-9, then add molysite, described molysite is one or more in ferrous sulfate, ferric sulfate, bodied ferric sulfate, poly-ferric chloride, ferric sulfate of polymerized silica, PPFS.
5. one as claimed in claim 1 contains in thallium heavy metal wastewater thereby and coagulation process for removing thallium, and it is characterized in that: in described step C, the filled media in strainer is one or more in activated carbon, zeolite, diatomite, manganese sand.
CN201410685459.XA 2014-11-25 2014-11-25 Process for removing thallium from thallium-containing heavy metal wastewater through neutralization and flocculation Pending CN104445732A (en)

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Cited By (15)

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Publication number Priority date Publication date Assignee Title
CN104803509A (en) * 2015-04-10 2015-07-29 深圳中清环境科技有限公司 Treatment process and treatment equipment for heavy metal wastewater containing thallium
CN105236619A (en) * 2015-10-15 2016-01-13 桂林市春晓环保科技有限公司 Method for removing heavy metal ions in water
CN105384288A (en) * 2015-11-23 2016-03-09 金川集团股份有限公司 System and method for treating acidic wastewater produced in acid making with smelting gas
CN105417794A (en) * 2015-12-14 2016-03-23 株洲冶炼集团股份有限公司 Microelectrolysis and coagulation linkage treatment device for thallium-containing heavy metal wastewater
CN105540946A (en) * 2015-12-14 2016-05-04 株洲冶炼集团股份有限公司 Process for removing thallium through microelectrolysis treatment of thallium-containing heavy metal wastewater
WO2016183947A1 (en) * 2015-05-20 2016-11-24 南京格洛特环境工程股份有限公司 Deep treatment method for polluted wastewater containing thallium and other heavy metal
CN106517587A (en) * 2016-11-30 2017-03-22 广东华欣环保科技有限公司 Thallium removing method for thallium-containing sintering flue gas desulfurization waste water
CN106517585A (en) * 2016-11-29 2017-03-22 湖南水口山有色金属集团有限公司 Method for staged removal of thallium from high thallium wastewater
CN107417004A (en) * 2017-05-19 2017-12-01 北京中科康仑环境科技研究院有限公司 A kind of method of advanced treating acid waste water containing thallium
CN109354328A (en) * 2018-12-10 2019-02-19 国家地质实验测试中心 A kind of acidic mine waste water processing system
CN110184466A (en) * 2019-05-31 2019-08-30 中运建设控股有限公司 A kind of method of valuable heavy metal extraction in water bodies of rivers and lakes
CN110194538A (en) * 2018-02-24 2019-09-03 湖南金蓝田环保工程有限公司 A method of the coordination grafting advanced treating of heavy metal wastewater thereby containing thallium
CN110745931A (en) * 2019-10-23 2020-02-04 北京科技大学 Method for treating composite heavy metal wastewater by coagulation-chemical precipitation
CN111620530A (en) * 2020-06-11 2020-09-04 南京师范大学 Reducing iron-sulfur mixed colloid, preparation method and application thereof
CN112408634A (en) * 2020-11-09 2021-02-26 九江德福科技股份有限公司 Process for treating zinc-copper-containing wastewater by using ferrous sulfate instead of calcium chloride

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CN103693819A (en) * 2014-01-02 2014-04-02 中南大学 Thallium-containing heavy metal wastewater advanced treatment method
CN103819023A (en) * 2014-02-28 2014-05-28 金川集团股份有限公司 Treatment and recycling method of industrial wastewater containing a plurality of heavy metal ions
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Cited By (17)

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Publication number Priority date Publication date Assignee Title
CN104803509A (en) * 2015-04-10 2015-07-29 深圳中清环境科技有限公司 Treatment process and treatment equipment for heavy metal wastewater containing thallium
WO2016183947A1 (en) * 2015-05-20 2016-11-24 南京格洛特环境工程股份有限公司 Deep treatment method for polluted wastewater containing thallium and other heavy metal
CN105236619A (en) * 2015-10-15 2016-01-13 桂林市春晓环保科技有限公司 Method for removing heavy metal ions in water
CN105384288B (en) * 2015-11-23 2017-12-01 金川集团股份有限公司 A kind of processing system and method for being used for acid waste water in metallurgical off-gas acid-making
CN105384288A (en) * 2015-11-23 2016-03-09 金川集团股份有限公司 System and method for treating acidic wastewater produced in acid making with smelting gas
CN105417794A (en) * 2015-12-14 2016-03-23 株洲冶炼集团股份有限公司 Microelectrolysis and coagulation linkage treatment device for thallium-containing heavy metal wastewater
CN105540946A (en) * 2015-12-14 2016-05-04 株洲冶炼集团股份有限公司 Process for removing thallium through microelectrolysis treatment of thallium-containing heavy metal wastewater
CN106517585A (en) * 2016-11-29 2017-03-22 湖南水口山有色金属集团有限公司 Method for staged removal of thallium from high thallium wastewater
CN106517587A (en) * 2016-11-30 2017-03-22 广东华欣环保科技有限公司 Thallium removing method for thallium-containing sintering flue gas desulfurization waste water
CN107417004A (en) * 2017-05-19 2017-12-01 北京中科康仑环境科技研究院有限公司 A kind of method of advanced treating acid waste water containing thallium
CN110194538A (en) * 2018-02-24 2019-09-03 湖南金蓝田环保工程有限公司 A method of the coordination grafting advanced treating of heavy metal wastewater thereby containing thallium
CN109354328A (en) * 2018-12-10 2019-02-19 国家地质实验测试中心 A kind of acidic mine waste water processing system
CN110184466A (en) * 2019-05-31 2019-08-30 中运建设控股有限公司 A kind of method of valuable heavy metal extraction in water bodies of rivers and lakes
CN110184466B (en) * 2019-05-31 2022-03-25 中运建设控股有限公司 Method for leaching valuable heavy metals in river and lake water body
CN110745931A (en) * 2019-10-23 2020-02-04 北京科技大学 Method for treating composite heavy metal wastewater by coagulation-chemical precipitation
CN111620530A (en) * 2020-06-11 2020-09-04 南京师范大学 Reducing iron-sulfur mixed colloid, preparation method and application thereof
CN112408634A (en) * 2020-11-09 2021-02-26 九江德福科技股份有限公司 Process for treating zinc-copper-containing wastewater by using ferrous sulfate instead of calcium chloride

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