CN105540946A - Process for removing thallium through microelectrolysis treatment of thallium-containing heavy metal wastewater - Google Patents
Process for removing thallium through microelectrolysis treatment of thallium-containing heavy metal wastewater Download PDFInfo
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- CN105540946A CN105540946A CN201510923293.5A CN201510923293A CN105540946A CN 105540946 A CN105540946 A CN 105540946A CN 201510923293 A CN201510923293 A CN 201510923293A CN 105540946 A CN105540946 A CN 105540946A
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- Prior art keywords
- thallium
- heavy metal
- microelectrolysis
- wastewater
- metal wastewater
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a process for removing thallium through microelectrolysis treatment of thallium-containing heavy metal wastewater. The process comprises a microelectrolysis part, a neutralization coagulation part and a sulfuric acid back adjustment part. The microelectrolysis treatment on the thallium-containing wastewater is performed through a high-activity microelectrolysis packing, and pretreatment thallium removal is performed; then the wastewater after microelectrolysis pretreatment thallium removal is subjected to acid-base adjustment and is adjusted to be alkaline, then a thallium removal agent and a flocculant are added successively, solid-liquid separation is performed through an inclined plate sedimentation tank, and thallium and heavy metal ions are removed; and finally sulfuric acid is used for adjusting and purifying water to be neutral, and then the wastewater is directly discharged to the outside. The process can effectively improve the removal rate of thallium and other heavy metal ions in the heavy metal wastewater, and prevents and controls the pollution of thallium and other heavy metal elements to a water environment.
Description
Technical field
The present invention relates to a kind of containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, relate to waste water containing thallium deep purifying treatment technology, comprise the complicated waste water containing thallium of contents of many kinds of heavy metal ion and the process of micro-waste water containing thallium, the invention belongs to containing thallium heavy metal containing wastewater treatment field.
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 copper, lead, zinc, cadmium, arsenic, thallium etc., they cannot be decomposed by organism, once will constantly accumulate in the environment after entered environment, severe contamination will be produced 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 humans and animals dead.
From the sixties in last century, potassium permanganate starts to be applied to waste water containing thallium processing technology field, has domesticly carried out systematic study to potassium permanganate except thallium technology in early 1980s.Potassium permanganate has strong oxidizing property, can by Tl
+be oxidized to Tl
3+, Tl precipitation is removed by recycling alkaline condition.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.Though this method has advantage simple to operate, have project investment large, the distinct disadvantage such as running cost is high, are difficult to form widespread use in heavy metal smelting wastewater field.
Patent CN102173517A discloses the method for thallium in a kind of polymer-based nano manganese oxide deep purifying water, and key step is: the pH value of the water of thallium pollution is adjusted to 5 ~ 8.5, then filters; Current after process, through being filled with packing tower or the filter bed of polymer-based nano manganese oxide, make thallium in water be adsorbed onto in this nano composite material by selectivity, stop absorption when thallium in filling adsorption water outlet reaches capacity value, adopt HCl and Ca (NO
3)
2mixing solutions carries out desorption and regeneration to the filler of polymer-based nano manganese oxide, and the filler after regeneration can Reusability.The method is applicable to compound wastewater and administers, and makes thallium content in water be down to 0.1 below μ g/L from 0.01-0.5mg/L.But the method is not suitable with the larger waste water of thallium content fluctuation, and there is the process Shortcomings in cost of investment and running maintenance convenience etc. for waste water containing thallium.
Adsorption method of separation is obvious to the removal effect of thallium ion in waste water, as the fractionation by adsorption utilizing various environment-friendly type sorbing material, environment mineral material or biological adsorption agent to carry out Tl in waste water, but the method is due to complex operation, the reasons such as compound wastewater bad adaptability and regneration of adsorbent material difficulty, are difficult to promote in actual industrial production process.
Salt precipitation method: saturated NaCl solution can impel the Tl in waste water
+effectively precipitate with TlCl form, but the method can increase the salt ionic concentration of waste water, cause the conductance of waste water higher, be unfavorable for follow-up film process, be also unfavorable for cycling utilization of wastewater, and NaCl consumption be very large.
Summary of the invention
The present invention is directed to the deficiency of existing single Technology, provide a kind of clean and effective, the one that simple to operate, preventing from heavy metal impact load ability is strong containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, its concrete technology comprise light electrolysis part, in and coagulation part and sulfuric acid readjustment part:
(1) light electrolysis part: carry out microelectrolysis processing to waste water containing thallium by high reactivity micro-electrolysis stuffing, carries out pre-treatment except thallium;
(2) with coagulation part in: carry out acid-alkali accommodation to the thallium heavy metal wastewater thereby that contains after microelectrolysis processing, be adjusted to alkalescence, then add de-thallium agent, flocculation agent successively, carry out solid-liquid separation finally by inclined plate sedimentation pond, remove thallium and heavy metal ion;
(3) sulfuric acid readjustment part: regulating purifies waste water to neutrality is directly outer afterwards arranges.
Further, the filler that described light electrolysis part uses is high reactivity micro-electrolysis stuffing, and the iron filings that described high reactivity micro-electrolysis stuffing uses in preparation process one or more modes in HCl treatment, carbonizing treatment, pulverization process activate.And add one or more in a certain amount of selenium slag, antimony slag, aluminium powder as catalyzer.
Further, described high reactivity micro-electrolysis stuffing composition mainly comprises the iron filings of 65wt% after hydrochloric acid activation process, the activated carbon powder of 25wt%, and the antimony slag of the selenium slag and 1wt% that add 1wt% is as catalyzer, and the clay of 8wt% is as binding agent.
Further, in and the neutralizing agent that uses in acid-alkali accommodation method described in coagulation part be milk of lime, one or more in sodium hydroxide or Wingdale, regulate pH to 9-11.
Further, be the organic synthesis reagent of sulfur-bearing with the de-thallium agent described in coagulation part in.
Further, in and the flocculation agent described in coagulation part be one or more in Polyferric Sulfate, poly-aluminium, polyacrylamide.
The invention has the advantages that: by waste water light electrolysis, in and coagulation except thallium, ensure that the degree of depth of thallium in waste water is removed, there is significant environmental benefit.The present invention is simple to operate, and except thallium efficiency is high, reagent cost is low, and preventing from heavy metal impact load ability is strong.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 containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium flow process according to of the present invention.
Embodiment
The present invention relates to a kind of containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, with containing thallium heavy metal wastewater thereby for handling object, by light electrolysis, in and the advanced treatment of coagulation and de-thallium agent, guarantee thallium and heavy metal element qualified discharge.Comprise light electrolysis part, in and coagulation part and sulfuric acid readjustment part:
(1) light electrolysis part: waste water containing thallium enters filler pond equably by water-distributing device, the electrochemical action produced by reduction and the microbattery of high reactivity micro-electrolysis stuffing, is reduced to thallium simple substance by the monovalence thallium ion in waste water.Again by the adsorption of high reactivity micro-electrolysis stuffing mesoporosity, by thallium simple substance Adsorption.Also a large amount of Fe can be produced in this partial reaction process
2+with Fe
3+.Described high reactivity micro-electrolysis stuffing composition mainly comprises the iron filings of 65wt% after hydrochloric acid activation process, the activated carbon powder of 25wt%, and the antimony slag of the selenium slag and 1wt% that add 1wt% is as catalyzer, and the clay of 8wt% is as binding agent.The microelectrolysis processing reaction times is 60-120 minute, in reaction process, carry out aeration with aerating apparatus, and aerating apparatus gas-water ratio is 5:1.
(2) with coagulation part in: the waste water containing thallium processed through filler pond enters swash plate first reaction tank, adds alkali lye in pond, regulate pH9-11, make the Tl in waste water
3+with Tl (OH)
3form formed solid sediment.The Fe produced in micro-electrolysis reaction process
2+form Fe (OH) in the basic conditions
2colloid, Fe
3+form Fe (OH) in the basic conditions
3colloid, two kinds of colloids produce coagulant precipitation effect and are fallen by the solid sediment sorption-coprecipitation of thallium and heavy metal.Waste water containing thallium after adjust ph enters swash plate second reaction tank, adds de-thallium agent in pond, de-thallium agent further with residual Tl in waste water
+with Tl
3+form solid sediment.Second reaction tank water outlet enters the 3rd reaction tank, in pond, add flocculation agent, and the solid sediment flocculation produced before is formed larger sediment cosedimentation.3rd reaction tank water outlet enters inclined-plate clarifying basin, carries out solid-liquid separation and removes the solid sediment of thallium and heavy metal, the discharge of inclined-plate clarifying basin standard water discharge or reuse.
(3) sulfuric acid readjustment part, with sulfuric acid in and purifying waste water after coagulating treatment carry out pH regulator, to regulate after pH6-9 directly outer row.
(4) enter sludge sump at the bottom of filler pond, swash plate reaction tank, inclined-plate clarifying basin, in sludge sump, mud adopts pump truck to take outward transport disposal away.
The present invention except thallium by waste water light electrolysis coagulation, be ensure that the degree of depth of thallium in waste water is removed, has significant environmental benefit.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.
It should be noted that, above-described embodiment is only for example of the present invention is clearly described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation still belong among protection scope of the present invention.
Claims (6)
1., containing a thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, it is characterized in that, comprise light electrolysis part, in and coagulation part and sulfuric acid readjustment part:
(1) light electrolysis part: carry out microelectrolysis processing to waste water containing thallium by high reactivity micro-electrolysis stuffing, carries out pre-treatment except thallium;
(2) with coagulation part in: carry out acid-alkali accommodation to the thallium heavy metal wastewater thereby that contains after microelectrolysis processing, be adjusted to alkalescence, then add de-thallium agent, flocculation agent successively, carry out solid-liquid separation finally by inclined plate sedimentation pond, remove thallium and heavy metal ion;
(3) sulfuric acid readjustment part: regulating purifies waste water to neutrality is directly outer afterwards arranges.
2. as claimed in claim 1 a kind of containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, it is characterized in that, the filler that described light electrolysis part uses is high reactivity micro-electrolysis stuffing, described high reactivity micro-electrolysis stuffing comprises iron filings, described iron filings one or more modes in preparation process in HCl treatment, carbonizing treatment, pulverization process activate, and add one or more in a certain amount of selenium slag, antimony slag, aluminium powder as catalyzer.
3. as claimed in claim 2 a kind of containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, it is characterized in that, described high reactivity micro-electrolysis stuffing composition mainly comprises the iron filings of 65wt% after hydrochloric acid activation process, the activated carbon powder of 25wt%, and the antimony slag of the selenium slag and 1wt% that add 1wt% is as catalyzer, the clay of 8wt% is as binding agent.
4. as claimed in claim 1 a kind of containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, it is characterized in that, in and the neutralizing agent that uses in acid-alkali accommodation method described in coagulation part be milk of lime, one or more in sodium hydroxide or Wingdale, regulate pH to 9-11.
5. as claimed in claim 1 a kind of to it is characterized in that containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, in and the de-thallium agent described in coagulation part be the organic synthesis reagent of sulfur-bearing.
6. as claimed in claim 1 a kind of to it is characterized in that containing thallium heavy metal wastewater thereby microelectrolysis processing process for removing thallium, in and the flocculation agent described in coagulation part be one or more in Polyferric Sulfate, poly-aluminium, polyacrylamide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510923293.5A CN105540946A (en) | 2015-12-14 | 2015-12-14 | Process for removing thallium through microelectrolysis treatment of thallium-containing heavy metal wastewater |
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| CN201510923293.5A CN105540946A (en) | 2015-12-14 | 2015-12-14 | Process for removing thallium through microelectrolysis treatment of thallium-containing heavy metal wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108380395A (en) * | 2018-02-28 | 2018-08-10 | 湘潭大学 | A kind of lead thallium separation method of the concentrate of lead sulfide ore containing thallium |
| CN114380462A (en) * | 2021-12-31 | 2022-04-22 | 德蓝(海南)未来之水有限公司 | Thallium removal method and wastewater treatment device |
| WO2023036053A1 (en) * | 2021-09-07 | 2023-03-16 | 中冶长天国际工程有限责任公司 | Cooperative treatment method and treatment system for high-salt solid waste ash and acidic wastewater of steel plant |
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| CN101643255A (en) * | 2009-09-07 | 2010-02-10 | 胡建忠 | Micro-electrolysis water-activating material and preparation method thereof |
| CN101948200A (en) * | 2010-09-10 | 2011-01-19 | 昆明理工大学 | Micro-electrolysis flocculation method for treating acid waste water containing heavy metals in mine |
| CN102531274A (en) * | 2010-12-31 | 2012-07-04 | 上海轻工业研究所有限公司 | Treatment method for ammonia nitrogen and COD (Chemical Oxygen Demand) in surface treatment waste water |
| CN104445732A (en) * | 2014-11-25 | 2015-03-25 | 株洲冶炼集团股份有限公司 | Process for removing thallium from thallium-containing heavy metal wastewater through neutralization and flocculation |
| CN105036413A (en) * | 2015-07-29 | 2015-11-11 | 广州市金龙峰环保设备工程有限公司 | Treatment process for wastewater containing thallium |
-
2015
- 2015-12-14 CN CN201510923293.5A patent/CN105540946A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643255A (en) * | 2009-09-07 | 2010-02-10 | 胡建忠 | Micro-electrolysis water-activating material and preparation method thereof |
| CN101948200A (en) * | 2010-09-10 | 2011-01-19 | 昆明理工大学 | Micro-electrolysis flocculation method for treating acid waste water containing heavy metals in mine |
| CN102531274A (en) * | 2010-12-31 | 2012-07-04 | 上海轻工业研究所有限公司 | Treatment method for ammonia nitrogen and COD (Chemical Oxygen Demand) in surface treatment waste water |
| CN104445732A (en) * | 2014-11-25 | 2015-03-25 | 株洲冶炼集团股份有限公司 | Process for removing thallium from thallium-containing heavy metal wastewater through neutralization and flocculation |
| CN105036413A (en) * | 2015-07-29 | 2015-11-11 | 广州市金龙峰环保设备工程有限公司 | Treatment process for wastewater containing thallium |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108380395A (en) * | 2018-02-28 | 2018-08-10 | 湘潭大学 | A kind of lead thallium separation method of the concentrate of lead sulfide ore containing thallium |
| WO2023036053A1 (en) * | 2021-09-07 | 2023-03-16 | 中冶长天国际工程有限责任公司 | Cooperative treatment method and treatment system for high-salt solid waste ash and acidic wastewater of steel plant |
| CN114380462A (en) * | 2021-12-31 | 2022-04-22 | 德蓝(海南)未来之水有限公司 | Thallium removal method and wastewater treatment device |
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Application publication date: 20160504 |