CN106517587A - Thallium removing method for thallium-containing sintering flue gas desulfurization waste water - Google Patents
Thallium removing method for thallium-containing sintering flue gas desulfurization waste water Download PDFInfo
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- CN106517587A CN106517587A CN201611081888.1A CN201611081888A CN106517587A CN 106517587 A CN106517587 A CN 106517587A CN 201611081888 A CN201611081888 A CN 201611081888A CN 106517587 A CN106517587 A CN 106517587A
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- thallium
- waste water
- reaction tank
- flue gas
- gas desulfurization
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a thallium removing method for thallium-containing sintering flue gas desulfurization waste water, and aims at solving the problems of an existing thallium removing method which is long in reaction time, unstable in thallium removing efficiency and high treatment cost. The thallium removing method comprises the following steps: adding alkali liquor to the waste water to regulate the pH of the waste water to be 9 to 10, so as to precipitate trivalent thallium in the waste water in a TI(OH)3 form; then adding industrial sodium sulfide to precipitate monovalent thallium (formula is as shown in the description) in the waste water; and finally adding a coagulant to completely coagulate the TI(OH)3 and TI2S precipitate so that the solid and liquid can be separated, thus achieving the purpose of fully removing thallium. The thallium removing method is simple in process, low in cost, high in removing rate and stable in system running; the concentration of heavy metal thallium in the sintering desulfurization waste water can be decreased to be 2 micrograms per liter or below, and thus the emission meeting the standard can be met.
Description
Technical field
The present invention relates to heavy metal containing wastewater treatment field, particularly to a kind of sintering flue gas desulfurization waste water containing thallium
Except thallium method.
Background technology
In tcrude ore and fire coal, the heavy metal such as thallium enters flue gas in sintering process, and enters in flue gas desulfurization, dust removal process
Waste water.Thallium is a kind of hypertoxic harmful substance, its toxicity far super As, Hg, Cd, Pb, Cu, and with certain savings, toxicity is made
Use the sustainable long period.Very harmful healthy to the common people of thallium pollution water body.Thallium has two kinds of oxidation state in nature：
T1+And Tl3+。T1+Compound property and alkali metal phase seemingly, it is soluble in water, it is difficult to natural subsidence.Thallium is hypertoxic metal, the product
According to《Safety management of dangerous chemical products regulations》By public security department's control.
Experts and scholars have substantial amounts of research report to the removal technique of thallium both at home and abroad at present, and main removal technique has
Three class such as chemical method, Physical and bioanalysises.Chemical method is to make the thallium in dissolved state in water be changed into insoluble heavy metal
Compound, Jing precipitations and floating upper method are removed from sewage；Physical be by the thallium in water under conditions of its chemical form is not changed,
Concentrated and separated；Bioanalysises are that preferred special strain is passed through in culture, thallium in water are enriched with using which, realize thallium
Removal.
Patent of invention CN1067229A discloses a kind of processing method of waste water containing thallium, and the method is to remove thallium with the sedimentation method,
It is characterized in that carrying out as follows；Add mineral acid first in waste water containing thallium, pH value is adjusted to 2-5, secondly add oxidation
Agent is T1+It is oxidized to Tl3+, Ca is added again2+Or Al3+Afterwards plus alkali heightening pH value formed Ca2+Or Al3+Precipitation, last precipitated liquid
1-6 hours discharge supernatant is placed, filtering residue is removed.
Patent of invention CN102107969A discloses a kind of emergency processing method of his polluted raw, comprises the following steps:
First, add a certain amount of potassium permanganate in raw water, or it is fully anti-with sodium hypochlorite to add a certain amount of potassium permanganate in raw water
Secondly answer more than 4 hours, the raw water of abundant reaction is passed through in haptoreaction pond, be passed through a certain amount of ozone and react 0.15～
0.25 hour, finally add aluminium polychlorid, thallium element in raw water is co-precipitated, filter, obtain meeting Drinking Water health
The drinking water of standard.
In sum, existing industrial wastewater is first except thallium method is mainly adds oxidant in waste water and ensures that oxidation is anti-
Should carry out completely, therefore the response time is longer, and the impact in view of other reproducibility ions in water body needs to add a large amount of oxygen
Agent, causes removal efficiency unstable and processing cost is higher.
The content of the invention
For solving above-mentioned technical problem, the present invention provide a kind of sintering flue gas desulfurization waste water containing thallium except thallium method, should
Method has process is simple, and low cost, clearance are high, and system run all right, can be by sintering desulfuration heavy metal in waste water thallium
Concentration is down to below 2 μ g/L, meets qualified discharge.
The present invention solves the scheme of above-mentioned technical problem：
A kind of processing method of the sintering flue gas desulfurization waste water containing thallium, the method are comprised the following steps：
（1）Liquid caustic soda is added in reaction tank 1（Mass fraction >=30% of sodium hydroxide）, consumption is 1.0～1.8 L/t；Persistently stir
After mixing 15min, the wastewater pH in reaction tank 1 is 9-10；
（2）Waste water in reaction tank 1 fully enters reaction tank 2, and adds in reaction tank 2 except thallium agent, described except thallium agent is work
Industry sodium sulfide（Mass fraction >=60% of sodium sulfide）, consumption is 0.8～1.5g/L；15min is stirred persistently；
（3）Waste water in reaction tank 2 fully enters reaction tank 3, and adds coagulant in reaction tank 3, the coagulant sulphuric acid
One kind in ferrous iron, ferric chloride, aluminium polychlorid, consumption are 1.1～2.0g/L, persistently stir 15min；
（4）Waste water fully enters settling zone, and overflow weir notch water outlet enters clear water reserviors, and filtrate enters the direct qualified discharge of clear water reserviors；
Sedimentation tank base sludge forms mud cake Jing after filter pressing, and outward transport is disposed.
Compared with prior art, it is an advantage of the current invention that：（1）Liquid caustic soda is added in sintering flue gas desulfurization waste water, is adjusted
PH to 9-10, makes the trivalent thallium in the waste water of reaction tank 1 with Tl (OH)3In the form of；Industrial sodium sulfide is added in waste water, is made
Monovalence thallium 2Tl in the waste water of reaction tank 2++ S2- = Tl2The coagulant added in S ↓ precipitate, with reaction tank 3（Sulphuric acid
One kind in ferrous iron, ferric chloride, aluminium polychlorid）Tl (OH) after reaction3、Tl2S precipitation flocculate completely, make solid-liquid separation so as to
Reach fully except the purpose of thallium.（2）Desulfurization wastewater containing thallium is processed to raw water thallium content no requirement (NR) by the invention, is removed by adjustment
The content of thallium agent and coagulant can make outer draining thallium content less than 2 μ g/L, qualified discharge.（3）This method need not be by monovalence
Thallium is oxidized to trivalent thallium, but directly catches coagulating sedimentation and remove, and operational approach principle is simple and removal effect is good.（4）This
Bright to use oxidant, the medicament totle drilling cost for being used is low, the cost for wastewater treatment of sintering flue gas desulfurization containing thallium control per ton
Within 7 yuan/ton.Certain steel mill just comes into operation in engineering at present.
Specific embodiment
The method of wastewater treatment of sintering desulfuration containing thallium of the present invention is further elaborated below by way of specific embodiment.
Embodiment 1
（1）Take 1000mL sintering desulfuration waste water（Thallium content is 800 μ g/L）In beaker, wastewater pH is adjusted to into more than 9 with liquid caustic soda,
Stirring reaction 15min；
（2）Weigh in 1.0g～1.5g sodium sulfide addition waste water, stirring reaction 15min；
（3）Weigh in 1.5g～2.0g ferrous sulfate addition waste water, after reaction 15min, after static 0.5h, take its supernatant.Sample
Product Jing environmental monitoring Spot detections, the clearance of thallium reach 99.92%.
Embodiment 2
In certain steel mill's sintering flue gas desulfurization wastewater treatment system operation, system process：Waste water → regulating reservoir → retort →
Pressure filter filter pressing → outer row.Before system operation, live employee will expire 30m on desulfurization wastewater3Retort is persistently stirred.（1）Anti-
Answer, after stirring reaction 15min, two bags are added except thallium agent（25kg/ bags）, after stirring reaction 15min,
It is eventually adding coagulant（50kg/ bags）, after stirring reaction 15min, all desulfurization wastewaters are carried out into whole filter pressings, pressure filter water
Sample thallium content after testing, detection filter pressing water thallium content are less than instrument Monitoring lower-cut（Less than 0.01 μ g/L）, calculate the clearance of thallium
For 100%
Embodiment 3
In certain steel mill's sintering flue gas desulfurization wastewater treatment system operation, system process：Waste water → horizontal sedimentation tank → regulation
Pond → one-level coagulating sedimentation tank → clear water reserviors → outer row.The adjusted pond elevator pump of desulfurization wastewater is heavy into one-level coagulating
Shallow lake pond, it is 9 to add liquid caustic soda to adjust desulfurization wastewater pH in reaction tank 1；It is 1.0～1.5g/ to add in reaction tank 2 except thallium agent concentration
L, adds coagulant concentration for 1.5～2.0g/L in reaction tank 3, and waste water enters precipitation zone, and overflow weir notch enters clear water reserviors,
To arrange outside clear water reserviors again, and detect thallium content, after testing outer draining sample, detection thallium content will be 0.298 μ g/L, and before processing sinters useless
Water thallium content is 479 μ g/L, and the clearance for calculating thallium is 99.93%.
Claims (5)
1. a kind of processing method of the sintering flue gas desulfurization waste water containing thallium, comprises the following steps：
（1）Liquid caustic soda is added in reaction tank 1（Mass fraction >=30% of sodium hydroxide）, consumption is 1.0～1.8 L/t；Persistently stir
After mixing 15min, the wastewater pH in reaction tank 1 is 9-10；
（2）Waste water in reaction tank 1 fully enters reaction tank 2, and adds in reaction tank 2 except thallium agent, described except thallium agent is work
Industry sodium sulfide（Mass fraction >=60% of sodium sulfide）, consumption is 0.8～1.5g/L；15min is stirred persistently；
（3）Waste water in reaction tank 2 fully enters reaction tank 3, and adds coagulant in reaction tank 3, consumption be 1.1～
2.0g/L, persistently stirs 15min；
（4）Waste water fully enters settling zone, and the water outlet of overflow weir notch is directly discharged after entering clear water reserviors.
2. a kind of processing method of the sintering flue gas desulfurization waste water containing thallium as claimed in claim 1, it is characterized by：The coagulation
Agent is ferrous sulfate.
3. a kind of processing method of the sintering flue gas desulfurization waste water containing thallium as claimed in claim 1, it is characterized by：The coagulation
Agent is ferric chloride.
4. a kind of processing method of the sintering flue gas desulfurization waste water containing thallium as claimed in claim 1, it is characterized by：The coagulation
Agent is aluminium polychlorid.
5. a kind of processing method of the sintering flue gas desulfurization waste water containing thallium as described in one of Claims 1-4, it is characterized by：
The sedimentation tank base sludge forms mud cake Jing after filter pressing, and mud cake outward transport is disposed.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611081888.1A CN106517587A (en) | 2016-11-30 | 2016-11-30 | Thallium removing method for thallium-containing sintering flue gas desulfurization waste water |
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| CN201611081888.1A CN106517587A (en) | 2016-11-30 | 2016-11-30 | Thallium removing method for thallium-containing sintering flue gas desulfurization waste water |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436674A (en) * | 2019-09-04 | 2019-11-12 | 湖南湘牛环保实业有限公司 | The minimum discharge treatment process of thallium in a kind of low concentration heavy metal water |
| CN110818128A (en) * | 2019-11-01 | 2020-02-21 | 郴州丰越环保科技有限公司 | Method for deeply removing thallium from high-ammonia-nitrogen and high-COD wastewater |
| CN112499892A (en) * | 2020-11-06 | 2021-03-16 | 白银有色红鹭资源综合利用科技有限公司 | Treatment method for synchronous deep removal of thallium-containing heavy metal wastewater |
| CN114735854A (en) * | 2022-04-20 | 2022-07-12 | 白银有色集团股份有限公司 | Device and method for treating thallium-containing wastewater in non-ferrous metal smelting |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103693819A (en) * | 2014-01-02 | 2014-04-02 | 中南大学 | Thallium-containing heavy metal wastewater advanced treatment method |
| 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 |
| CN106145451A (en) * | 2016-08-24 | 2016-11-23 | 湖南省环境保护科学研究院 | A kind of processing method of waste water containing thallium |
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2016
- 2016-11-30 CN CN201611081888.1A patent/CN106517587A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693819A (en) * | 2014-01-02 | 2014-04-02 | 中南大学 | Thallium-containing heavy metal wastewater advanced treatment method |
| 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 |
| CN106145451A (en) * | 2016-08-24 | 2016-11-23 | 湖南省环境保护科学研究院 | A kind of processing method of waste water containing thallium |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436674A (en) * | 2019-09-04 | 2019-11-12 | 湖南湘牛环保实业有限公司 | The minimum discharge treatment process of thallium in a kind of low concentration heavy metal water |
| CN110436674B (en) * | 2019-09-04 | 2022-04-12 | 湖南湘牛环保实业有限公司 | Ultralow-emission treatment process for thallium in low-concentration heavy metal wastewater |
| CN110818128A (en) * | 2019-11-01 | 2020-02-21 | 郴州丰越环保科技有限公司 | Method for deeply removing thallium from high-ammonia-nitrogen and high-COD wastewater |
| CN112499892A (en) * | 2020-11-06 | 2021-03-16 | 白银有色红鹭资源综合利用科技有限公司 | Treatment method for synchronous deep removal of thallium-containing heavy metal wastewater |
| CN114735854A (en) * | 2022-04-20 | 2022-07-12 | 白银有色集团股份有限公司 | Device and method for treating thallium-containing wastewater in non-ferrous metal smelting |
| CN114735854B (en) * | 2022-04-20 | 2023-10-24 | 白银有色集团股份有限公司 | Device and method for treating thallium-containing wastewater in nonferrous metal smelting |
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Application publication date: 20170322 |
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