CN106746024A - A kind of processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium - Google Patents
A kind of processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium Download PDFInfo
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- CN106746024A CN106746024A CN201710055206.8A CN201710055206A CN106746024A CN 106746024 A CN106746024 A CN 106746024A CN 201710055206 A CN201710055206 A CN 201710055206A CN 106746024 A CN106746024 A CN 106746024A
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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
- C02F1/00—Treatment of water, waste water, or sewage
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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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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a kind of processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium.Prepare the mixed solution A and flocculant solution B of dissolvable sulfide and soluble carbonate salt with running water respectively first, then add flocculant solution B after Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium first adds mixed solution A to react a period of time to precipitate, supernatant is the waste water after treatment.The present invention is processed Ferrous Metallurgy sintering flue gas desulfurization waste water using co-precipitation and hindered falling principle and method, and with process is simple, removal efficiency is high, the features such as low cost, can be by the Tl in waste water+Ion concentration is removed to below 5 μ g/L from 1,000 10000 μ g/L, and efflux wastewater can reach Hunan Province《Industrial wastewater thallium pollution thing discharge standard（DB43/968‑2014）》It is required that, it is a kind of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium New Method for Processing with good industrial application value.
Description
Technical field
The invention belongs to water-treatment technology field, at waste water of the Ferrous Metallurgy sintering flue gas desulfurization containing thallium
Reason.
Background technology
In the sintering process of Ferrous Metallurgy iron ore, due in iron ore often with various poisonous and hazardous micro
Or trace heavy metal compound（Such as Determination of Trace Thallium, trace zinc, lead, copper etc.）, therefore in its high temperature sintering, these poisonous and harmful weights
Metallic compound can together enter sintering flue gas desulfurization system because gasifying or distilling phenomenon in company with high-temperature flue gas.Sintering flue gas takes off
Although alkaline absorption solution in sulphur system has certain precipitation removal to act on to these micro or trace heavy metal ions, but due to
The ionic equilibrium limitation of precipitation reaction（That is the solubility product limitation of chemical precipitation）So that these heavy metal ion cannot be more complete
Removing and be still in absorbing liquid.For closed circuit or half closed-circulation type sintering flue gas desulfurization system, part it is micro or
Trace heavy metal ion can progressively be enriched with the recycled for multiple times of alkaline absorption solution, form poisonous with higher concentration
Even hypertoxic heavy metal desulfurization waste liquor.Meanwhile, in the actual motion of sintering flue gas desulfurization, for the ionic equilibrium for maintaining system is closed
System, often need will outside least a portion of this desulfurization waste liquor arrange, thus cause containing Determination of Trace Thallium severe toxicity heavy metal and containing trace zinc,
The high safety harm and environment risk problem high for bringing are arranged outside the poisonous and harmful heavy metallic waste water such as lead, copper.According to creation data point
Analysis, Tl in the desulfurization waste liquor of outer row+Concentration is about 1.0-10.0 mg/L, meanwhile, also it is about containing total mass concentration in waste liquid
The Ca of 0.5%-1.0%2+、Mg2+Deng the sulfuric acid or sulphite of other metal ions.
Thallium is that Environmental Protection Agency lists one of 13 kinds of heavy metal contaminants of preferential monitoring in, is also China《It is heavy metal-polluted
Dye integrated control " 12 " planning》Take into account one of heavy metal contaminants of preventing and treating.Relevant research shows, intoxicating of the thallium in water
Concentration is 0.5 μ g/L.China specifies that the safe level of soluble thallium compound is 0.1mg/m in air at present3, in surface water
The content standard of thallium is below 0.1 μ g/L.Though current China does not make the national standard of thallium concentration of emission to commonly industrial wastewater
Regulation, but it belongs to the pollutant and danger of strict control discharge.It is dirty that Hunan Province has formulated industrial wastewater thallium for 2014
The provincial standard of dye thing discharge（DB43/ 968—2014）And the formal implementation from 1 day January in 2015.The standard specifies：Relate to thallium
In industrial wastewater, the limit value of thallium pollution thing discharge within 5 μ g/L, the waste water that all She Tuo industrial enterprises directly or indirectly discharge
Performed according to this regulation without exception.
Research report at present for waste water containing thallium processing method is more, mainly includes：1. Strong oxdiative coagulant sedimentation；②
Ion-exchange；3. absorption method；4. salting out method etc..
Strong oxdiative coagulant sedimentation is that the monovalence thallium of stable existence in waste water is oxidized into unstable trivalent thallium, then makes it
Generation Tl (OH) in the basic conditions3And Tl2O3Precipitation, its technique is mainly adjusted including pH, Strong oxdiative, the step such as coagulation/flocculation
Suddenly, processing procedure is relatively complicated, time-consuming, drug consumption is big, simultaneously because the trivalent thallium toxicity formed after oxidation is bigger, stabilization
Property is poor so that the technology is industrially difficult to be used widely；Ion exchange rule in sintering flue gas desulfurization waste water due to containing
There is the Na of higher concentration+、K+、Ca2+、Mg2+、Pb2+、Zn2+、Cu2+Deng cation so that resin is competing to trace Tl ion selectivities
Exchange capacity variation is striven, simultaneously because the absorption exchange equilibrium/saturated capacity of resin is smaller, thus its removal efficiency is low, treatment
Tl ions are difficult to up to standard in waste water afterwards, and cost for wastewater treatment is higher；Although absorption method has process is simple, easy to operate etc. excellent
Point, but adsorbent amount is larger, it is cumbersome to regenerate, and treatment effect is undesirable and relatively costly.Salting out method is used in waste water
Adding the method for a large amount of NaCl makes wherein Tl+Precipitated in the form of TlCl and be able to what is removed.But a large amount of of NaCl use, meeting
Increase the salinity and corrosivity of waste water, meanwhile, high salinity waste water is also difficult to be circulated or recycles.Therefore, research and develop a kind of de-
Except efficiency high, processing cost are low, the simple Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium processing method of technological process has weight
The realistic meaning and industrial application value wanted.
It can be seen from principle is co-precipitated：When two or more material is precipitated simultaneously, can occur between sediment
Adsorption, mutually contain and acted on mixed crystal etc., these effects may advantageously facilitate precipitation system small particles material and dredge with having
Pine, the aggregation of the cotton-shaped suspension of loose structure；Meanwhile, it can be seen from hindered falling principle：It is appropriate to be added in precipitation system
Flocculant, the interference effect between settling particulate matter can be strengthened, so as to promote the growth of grain graininess, the sedimentation of increase products
Speed, reaches quick, the purpose that efficiently separates of solid-liquid.
Therefore, using Tl+Strong close sulphur（S2-）Property and Tl2The precipitation solubility product very little of S（Ksp=5×10-21）Spy
Point, dissolvable sulfide is added in above-mentioned sintering flue gas desulfurization waste water containing thallium（First precipitating reagent）, Tl therein can be made+With S2-
Act on and more fully generate Tl2S is precipitated.In view of Tl+Concentration is very low in above-mentioned waste water, and it is generated after being acted on sulfide
Tl2S sediment total amounts are few, granularity is small, may cause thallium in the waste water after its, treatment more difficult with the solid- liquid separation of waste water
Pollutant is still difficult to the actual conditions of qualified discharge, to promote Tl2Precipitation, the separating effect of S and waste water, to above-mentioned waste water body
System adds dissolvable sulfide（First precipitating reagent）While, resynchronisation adds soluble carbonate salt（Second precipitating reagent）So that useless
Part Ca in water2+、Mg2+A certain amount of carbonate sediment is formed, and makes these Ca2+、Mg2+Carbonate sediment with
Tl2S produces co-precipitation effect.Then, appropriate flocculant is added by waste water system, makes to be produced between above-mentioned co-precipitate
Flocculation interference precipitation, so as to realize micro Tl in waste water+、Ca2+、Mg2+、Pb2+、Zn2+、Cu2+Plasma it is quick, efficient
Removal.
The present invention in Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium using adding dissolvable sulfide and solvable simultaneously
The method of acid carbonate, makes the Tl in waste water+ 、Pb2+、Zn2+、Cu2+Deng pollutant and S2-And CO3 2-Generate corresponding slightly solubility
Heavy metal sulfide, carbonate deposition, the Ca in waste water2+、Mg2+With CO3 2-The calcium carbonate and magnesium carbonate precipitation of indissoluble is generated, so that real
Various metals cation and S in waste water system are showed2-And CO3 2-Deng the interactive Sunk-fund effect between anion；By to precipitation body
The method that system adds flocculant, efficient, quick point that solid-liquid mixed system is strengthened so as to reach using hindered falling principle
From purpose.
The inventive method is to Tl in Ferrous Metallurgy sintering flue gas desulfurization waste water+、Pb2+、Zn2+、Cu2+Deng heavy metal contaminants
Processed, with process is simple, removal efficiency is high, low cost the features such as, be a kind of steel with good industrial application value
Iron metallurgy sintering smoke desulfurization waste water containing thallium New Method for Processing.
The content of the invention
The present invention proposes a kind of processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium, and its technical scheme is included such as
Lower step：
（1）The mixed solution A of dissolvable sulfide and soluble carbonate salt is prepared with running water；
（2）Flocculant solution B is prepared with running water；
（3）Under room temperature and stirring condition, to mixed solution A is added in Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium, carry out
Reaction；
（4）Under room temperature and stirring condition, to step（3）Flocculant solution B is added in resulting solution, is staticly settled after stirring,
Then will be arranged outside supernatant waste water；Useless water sample analysis are taken, Tl in processed waste water is calculated as follows+Clearance R：
In formula：Tl in R-waste water+Clearance（%）；
Tl in C-processed waste water+Concentration（ppm）；
C0Tl in-before processing waste water+Concentration（ppm）.
Further, Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium also contains Ca2+、Mg2+、Pb2+、Zn2+、Cu2+Deng from
Son.
Further, described dissolvable sulfide be vulcanized sodium, potassium sulfide one or two, preferred vulcanized sodium；Institute
State soluble carbonate salt for sodium carbonate, potassium carbonate one or two, preferred sodium carbonate.
Further, step（1）In, the mass concentration of dissolvable sulfide in mixed solution A（Mass fraction）It is 2.0-
4.0%, preferably 2.5%；The mass concentration of soluble carbonate salt is 10.0-17.0%, preferably 15.0%.
Further, step（2）In, flocculant solution B is polyacrylamide（PAM）, the chloride or sulfuric acid of aluminium or iron
Salt, or one or more of their polymer the aqueous solution, preferred polyacrylamide（PAM）.
Further, step（2）In, the mass concentration of flocculant is 1.0-3.0%, preferably 2.0% in flocculant solution B.
Further, step（3）In, speed of agitator is 60-180rpm, preferably 150 rpm；The addition of mixed solution A
It is 50-100mL/L waste water, preferably 150mL/L；Reaction time is 10-30min, preferably 20min.
Further, step（4）In, speed of agitator is 40-80rpm, preferably 60 rpm；The addition of flocculant solution B
It is 1.0-5.0mL/L waste water, preferably 2mL/L；Mixing time is 5-15min, preferably 8min；Time of repose is 30-60min, excellent
Select 40min.
The beneficial effects of the present invention are：
The present invention utilizes co-precipitation and hindered falling principle and method, to Tl in Ferrous Metallurgy sintering flue gas desulfurization waste water+、Pb2+、
Zn2+、Cu2+Processed Deng heavy metal contaminants, with process is simple, removal efficiency is high, can be by the Tl in waste water+Ion concentration
It is removed to below 5 μ g/L from 1000-10000 μ g/L, the clearance to thallium is close absolutely, and processing cost is low, outer row
Waste water can reach Hunan Province《Industrial wastewater thallium pollution thing discharge standard（DB43/ 968-2014）》It is required that, it is that one kind has well
The Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium New Method for Processing of industrial application value.
Specific embodiment
To more fully understand the present invention, further specific elaboration is made to the present invention below by following examples, but not
Limitation of the invention is can be regarded as, it is nonessential according to some that foregoing invention content is made for those skilled in the art
Improve and adjust, be also considered as being within the scope of the present invention.
Embodiment 1
The well mixed sintering flue gas desulfurization waste water that 1000mL concentration containing thallium is 3.50mg/L is taken, in 150rpm speeds of agitator
Under, contain Na in wherein adding2S and containing Na2CO3Mass concentration is respectively 3.0% and 12.5% mixed solution 75mL, reacts 20min
Afterwards, speed of agitator is down to 60rpm, then the polyacrylamide that mass concentration is 2.0% is added in waste water（PAM）Flocculant is molten
Liquid 4.0mL, stirs 12min, stands 50min, takes the supernatant after precipitate and separate and analyzes thallium concentration therein using ICP-Mass
It is 2.80 μ g/L, is calculated Tl in processed waste water+Clearance R be 99.92%.
Embodiment 2
The well mixed sintering flue gas desulfurization waste water that 800mL concentration containing thallium is 2.0mg/L is taken, under 180rpm speeds of agitator,
Contain K in wherein adding2S and containing K2CO3Mass concentration is respectively 4.0% and 11.5% mixed solution 60mL, after reaction 15min, will
Speed of agitator is down to 40rpm, then the polyacrylamide that mass concentration is 1.0% is added in waste water（PAM）Flocculant solution
3.0mL, stirs 10min, stands 40min, take the supernatant after precipitate and separate use ICP-Mass analysis thallium concentration therein for
3.60 μ g/L, are calculated Tl in processed waste water+Clearance R be 99.82%.
Embodiment 3
The well mixed sintering flue gas desulfurization waste water that 2000mL concentration containing thallium is 8.0mg/L is taken, under 120rpm speeds of agitator,
Contain K in wherein adding2S and containing Na2CO3Mass concentration is respectively 2.0% and 14.0% mixed solution 150mL, after reaction 20min,
Speed of agitator is down to 60rpm, then the bodied ferric sulfate that mass concentration is 2.0% is added in waste water（PFS）Flocculant solution
10.0mL, stirs 12min, stands 60min, take the supernatant after precipitate and separate use ICP-Mass analysis thallium concentration therein for
4.70 μ g/L, are calculated Tl in processed waste water+Clearance R be 99.94%.
Embodiment 4
The well mixed sintering flue gas desulfurization waste water that 1000mL concentration containing thallium is 5.0mg/L is taken, under 150rpm speeds of agitator,
Contain Na in wherein adding2S and containing K2CO3Mass concentration is respectively 3.0% and 12.5% mixed solution 75mL, after reaction 25min,
Speed of agitator is down to 40rpm, then the polyacrylamide that mass concentration is 2.0% is added in waste water（PAM）Flocculant solution
5.0mL, stirs 15min, stands 55min, take the supernatant after precipitate and separate use ICP-Mass analysis thallium concentration therein for
4.60 μ g/L, are calculated Tl in processed waste water+Clearance R be 99.91%.
Embodiment 5
The well mixed sintering flue gas desulfurization waste water that 500mL concentration containing thallium is 10.0mg/L is taken, under 120rpm speeds of agitator,
Contain Na in wherein adding2S and containing Na2CO3Mass concentration is respectively 4.0% and 12.0% mixed solution 45mL, after reaction 20min,
Speed of agitator is down to 60rpm, then adds the poly- h that mass concentration is 2.0% to close aluminium chloride in waste water（PAC）Flocculant solution
3.0mL, stirs 12min, stands 40min, take the supernatant after precipitate and separate use ICP-Mass analysis thallium concentration therein for
3.90 μ g/L, are calculated Tl in processed waste water+Clearance R be 99.96%.
Embodiment 6
The well mixed sintering flue gas desulfurization waste water that 1000mL concentration containing thallium is 1.5mg/L is taken, under 100rpm speeds of agitator,
Contain Na in wherein adding2S and containing Na2CO3Mass concentration is respectively 2.5% and 15.0% mixed solution 65mL, after reaction 25min,
Speed of agitator is down to 60rpm, then the bodied ferric sulfate that mass concentration is 3.0% is added in waste water（PFS）Flocculant solution
3.0mL, stirs 10min, stands 50min, take the supernatant after precipitate and separate use ICP-Mass analysis thallium concentration therein for
4.20 μ g/L, are calculated Tl in processed waste water+Clearance R be 99.72%.
Above content is to combine specific preferred embodiment further description made for the present invention, is not used to
The limitation present invention, it is all also to make some simple deduction or replace without departing from the inventive concept of the premise, should all be considered as
Belong to protection scope of the present invention.
Claims (8)
1. a kind of processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium, it is characterised in that comprise the following steps：
（1）The mixed solution A of dissolvable sulfide and soluble carbonate salt is prepared with running water；
（2）Flocculant solution B is prepared with running water；
（3）Under room temperature and stirring condition, to mixed solution A is added in Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium, carry out
Reaction；
（4）Under room temperature and stirring condition, to step（3）Flocculant solution B is added in resulting solution, is staticly settled after stirring,
To be arranged outside supernatant waste water.
2. the processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium according to claim 1, it is characterised in that institute
The Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium stated also contains Ca2+、Mg2+、Pb2+、Zn2+、Cu2+Ion.
3. the processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium according to claim 1 and 2, its feature exists
In step（1）In, described dissolvable sulfide is vulcanized sodium, potassium sulfide one or two；Described soluble carbonate salt
For sodium carbonate, potassium carbonate one or two.
4. the processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium according to claim 1 and 2, its feature exists
In step（1）In, the mass concentration of described dissolvable sulfide is 2.0 ~ 4.0%；The quality of described soluble carbonate salt
Concentration is 10.0 ~ 17.0%.
5. the processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium according to claim 1 and 2, its feature exists
In step（2）In, flocculant solution B is polyacrylamide PAM, the chloride or sulfate of aluminium or iron, or their polymer
One or more the aqueous solution.
6. the processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium according to claim 1 and 2, its feature exists
In step（2）In, the mass concentration of flocculant is 1.0-3.0% in flocculant solution B.
7. the processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium according to claim 1 and 2, its feature exists
In step（3）In, speed of agitator is 60-180rpm；The addition of mixed solution A is 50-100mL/L waste water；Reaction time is
10-30min。
8. the processing method of Ferrous Metallurgy sintering flue gas desulfurization waste water containing thallium according to claim 1 and 2, its feature exists
In step（4）In, speed of agitator is 40-80rpm；The addition of flocculant solution B is 1.0-5.0mL/L waste water；Mixing time
It is 5-15min；Time of repose is 30-60min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658301A (en) * | 2018-06-12 | 2018-10-16 | 安徽工业大学 | A kind of industrial wastewater removes thallium method except the precipitating reagent and industrial wastewater depth of thallium |
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| CN108658301A (en) * | 2018-06-12 | 2018-10-16 | 安徽工业大学 | A kind of industrial wastewater removes thallium method except the precipitating reagent and industrial wastewater depth of thallium |
| CN108658301B (en) * | 2018-06-12 | 2020-12-15 | 安徽工业大学 | Precipitant for industrial wastewater thallium removal and industrial wastewater deep thallium removal method |
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