CN104692561B - Advanced treatment method of thallium-containing wastewater - Google Patents

Advanced treatment method of thallium-containing wastewater Download PDF

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Publication number
CN104692561B
CN104692561B CN201510106618.0A CN201510106618A CN104692561B CN 104692561 B CN104692561 B CN 104692561B CN 201510106618 A CN201510106618 A CN 201510106618A CN 104692561 B CN104692561 B CN 104692561B
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China
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waste water
thallium
wastewater
concentration
sulfide
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CN104692561A (en
Inventor
杨晓松
胡建龙
邵立南
郑曦
陈国强
刘峰彪
刘艳丽
赵少康
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Beijing General Research Institute of Mining and Metallurgy
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Beijing General Research Institute of Mining and Metallurgy
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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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone

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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)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a deep treatment method of thallium-containing wastewater, which comprises the steps of firstly, adding sodium sulfide and iron sulfide seed crystals into thallium-containing wastewater in a grading manner, so that high-concentration heavy metals in the wastewater form sulfide precipitates, and preliminarily reducing the concentration of the heavy metals in the wastewater; adding a certain amount of advanced oxidant into the wastewater after the sulfurization precipitation treatment, and carrying out oxidation treatment on thallium in the wastewater to change the form of thallium in the wastewater; and conveying the wastewater after the advanced oxidation treatment to an adsorption tower filled with a nano hydrated manganese oxide adsorbent, and further deeply removing trace heavy metals remained in the wastewater through the strong adsorption capacity of the nano hydrated manganese oxide adsorbent. The treatment method improves thallium removal efficiency and treatment efficiency of rear-end deep adsorption treatment, is beneficial to treatment and reuse of thallium-containing wastewater, and has important significance for emission reduction of total heavy metal pollutants in areas with low heavy metal environmental capacity.

Description

A kind of deep treatment method of waste water containing thallium
Technical field
The present invention relates to heavy metal processing technology field, more particularly to a kind of deep treatment method of waste water containing thallium.
Background technology
At present, thallium is very low in the abundance of nature, but its toxicity is but much larger than heavy metal, thallium and its changes such as Hg, Cd, As Compound be put into water body priority pollutants blacklist and《Water environment quality standard (GB838-2002)》Monitoring Index system.In industrial waste water treatment containing thallium, because industrial wastewater containing thallium has the spies such as high salinity, high reproducibility Point, using treatment technologies such as conventional neutralization precipitation, sulfide precipitations, it is difficult to realize that the depth of the heavy metals such as thallium is removed.
The wastewater processing technology such as conventional neutralization precipitation, sulfide precipitation in prior art, due to the presence of salt effect, The solubility of thallium precipitation can be improved so that thallium concentration is significantly higher than theoretical value in precipitation water outlet.And use existing ion exchange Deng conventional absorbtion treatment technology, then due to the presence of the competitive cation such as calcium, magnesium, sodium of Coal Gas Washing Cycling Water, make adsorbent It is rapidly achieved adsorption saturation state so that adsorption column frequent regeneration, reduces the practicality of technology.
The content of the invention
It is an object of the invention to provide a kind of deep treatment method of waste water containing thallium, the processing method is improved except thallium effect Rate, and rear end depth adsorption treatment treatment effeciency, not only contribute to reuse after the processing of waste water containing thallium, and for a huge sum of money Belong to the low regional heavy metal contaminants total amount emission reduction of environmental carrying capacity significant.
A kind of deep treatment method of waste water containing thallium, methods described includes：
Step 1, into waste water containing thallium classification add vulcanized sodium and iron sulfide crystal seed, make high concentration in the waste water with much money Category forms sulfide precipitation, tentatively reduces the heavy metal concentration in the waste water；
Step 2, handled to sulfide precipitation after waste water in, a certain amount of advanced oxidation agent is added, to the thallium in waste water Oxidation processes are carried out, change the form of thallium in waste water；
Step 3, advanced oxidation is handled after waste water be delivered to the absorption for being filled with nano hydrated manganese oxide sorbents Tower, it is by the strong adsorption capacity of the nano hydrated manganese oxide sorbents, the micro heavy remained in waste water is further deep Degree is removed.
As seen from the above technical solution provided by the invention, the processing method is improved except thallium efficiency, and rear end The treatment effeciency of depth adsorption treatment, not only contributes to reuse after the processing of waste water containing thallium, and for heavy metal environmental carrying capacity Low regional heavy metal contaminants total amount emission reduction is significant.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, being used required in being described below to embodiment Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings Accompanying drawing.
The waste water containing thallium deep treatment method schematic flow sheet that Fig. 1 is provided by the embodiment of the present invention.
Embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Ground is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this The embodiment of invention, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made Example, belongs to protection scope of the present invention.
The embodiment of the present invention is described in further detail below in conjunction with accompanying drawing, is as shown in Figure 1 present invention implementation The waste water containing thallium deep treatment method schematic flow sheet that example is provided, methods described includes：
Step 1, into waste water containing thallium classification add vulcanized sodium and iron sulfide crystal seed, make high concentration in the waste water with much money Category forms sulfide precipitation, tentatively reduces the heavy metal concentration in the waste water；
Sulfide precipitation processing is carried out to waste water containing thallium in this step first, can also be right before sulfide precipitation processing The waste water carries out complete water quality analysis, obtains the concentration of the heavy metal (Tl, Pb, Zn, As, Cd etc.) in the waste water, calculates To the theoretical dosage of sulfide needed for the heavy metal in waste water sulfide precipitation, specific dosage is：
Between 10~20 times of theoretical dosage for needed for the heavy metal in waste water sulfide precipitation of the dosage of vulcanized sodium, And preferably 15 times；
The dosage of iron sulfide crystal seed is 1~1.3 times of the vulcanized sodium dosage, and preferably 1.2 times；
Further, after vulcanized sodium and iron sulfide crystal seed is added：
The stirring reaction time is and preferably 15min between 10min~30min；
The precipitation reaction time is and preferably 3h between 2h~4h；
The bed mud of sulfide precipitation is partly refluxed to first order sulfide precipitation reaction tank, and reflux ratio is 2~3:Between 1.
Step 2, handled to sulfide precipitation after waste water in, a certain amount of advanced oxidation agent is added, to the thallium in waste water Oxidation processes are carried out, change the form of thallium in waste water；
In this step, the advanced oxidation agent added includes：Sodium hypochlorite, hydrogen peroxide or potassium permanganate, and it is preferably secondary Sodium chlorate and potassium permanganate；
And the dosage of the advanced oxidation agent is 1.2~1.5 times of sulfide dosage；
The time of oxidation reaction is and preferably 15min between 5min~30min.
Step 3, advanced oxidation is handled after waste water be delivered to the absorption for being filled with nano hydrated manganese oxide sorbents Tower, it is by the strong adsorption capacity of the nano hydrated manganese oxide sorbents, the micro heavy remained in waste water is further deep Degree is removed.
In this step, the micro heavy of residual mainly includes thallium, lead, zinc etc.；The operation filtering velocity of the adsorption tower is 7 The concentration of heavy metal ion such as thallium, lead, zinc can reach water environment quality standard in water outlet after~15m/h, and final process Concentration limit requirement.
In the specific implementation, the preparation method of the nano hydrated manganese oxide sorbents includes：
Prepare first and contain Manganous sulfate monohydrate MnSO4.H2O, disodium ethylene diamine tetraacetate EDTA-Na2, nitric acid HNO3's Initial manganese solution, wherein the MnSO4.H2O concentration is 0.5%~2%, the EDTA-Na2Concentration for 0.1%~ 0.3%, the HNO3Concentration is 2%~4%；
Mass concentration is added into the initial manganese solution again and is 0~40% cationic ion-exchange resin, and soaks reaction 1 ~2h；Wherein described cationic ion-exchange resin includes：D001, D402 or 001 type ion exchange resin；
Then KMnO is added4Solution, generates the nano hydrated manganese oxide sorbents；The KMnO wherein added4Solution For MnSO in the initial manganese solution4.H21~1.1 times of O amounts.
Thus can be by EDTA-Na2Chelation, be prevented effectively from the nano hydrated manganese oxide sorbents of generation Reunite, so as to improve its adsorption capacity.
In summary, the processing method described in the embodiment of the present invention has the following advantages that：
(1) handled, reduced except the salt effect of precipitation reaction during thallium with introducing crystal seed by the multi stage precipitation of vulcanization, Improve sulfurization-precipitation method removes thallium efficiency, improves the technology resisting high-concentration impact load and processivity.
(2) handled by advanced oxidation, change the existing forms of thallium in waste water, improve rear end depth adsorption treatment Treatment effeciency.
(3) after this method processing water outlet can reach relevant industries or place for efflux wastewater thallium concentration limit requirement or Water environment quality standard (GB3838-2002) requirement, with the removal efficiency of heavy metals such as thallium height, is invested and operating cost phase To it is relatively low the characteristics of.
(4) processing method belongs to after heavy metal-containing waste water further treatment technique, processing that heavy metal concentration is low in water outlet, no Only be conducive to reuse after the processing of waste water, and for the low regional heavy metal contaminants total amount emission reduction of heavy metal environmental carrying capacity It is significant.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in, It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims Enclose and be defined.

Claims (4)

1. a kind of deep treatment method of waste water containing thallium, it is characterised in that methods described includes：
Step 1, into waste water containing thallium classification add vulcanized sodium and iron sulfide crystal seed, make the high concentration heavy metal shape in the waste water Sulphidisation is precipitated, and tentatively reduces the heavy metal concentration in the waste water；
Wherein, before the operation of the step 1 is carried out, methods described also includes：
Complete water quality analysis is carried out to the waste water, the heavy metal concentration in the waste water is obtained, calculating obtains weight in the waste water The theoretical dosage of sulfide needed for metal sulfide precipitation；
Further, in the step 1：The dosage of vulcanized sodium is theoretical for needed for the heavy metal in waste water sulfide precipitation to be thrown 10~20 times of dosage；The dosage of iron sulfide crystal seed is 1~1.3 times of the vulcanized sodium dosage；Add vulcanized sodium with After iron sulfide crystal seed：The stirring reaction time is 10min~30min；The precipitation reaction time is 2h~4h；The bed mud of sulfide precipitation First order sulfide precipitation reaction tank is partly refluxed to, and reflux ratio is 2~3:1；
Step 2, handled to sulfide precipitation after waste water in, add a certain amount of advanced oxidation agent, in waste water thallium carry out Oxidation processes, change the form of thallium in waste water；
Step 3, advanced oxidation is handled after waste water be delivered to the adsorption tower for being filled with nano hydrated manganese oxide sorbents, lead to The strong adsorption capacity of the nano hydrated manganese oxide sorbents is crossed, the further depth of the micro heavy remained in waste water is gone Remove.
2. the deep treatment method of waste water containing thallium according to claim 1, it is characterised in that in the step 2：
The advanced oxidation agent added includes：Sodium hypochlorite, hydrogen peroxide or potassium permanganate；
And the dosage of the advanced oxidation agent is 1.2~1.5 times of sulfide dosage；
The time of oxidation reaction is 5min~30min.
3. the deep treatment method of waste water containing thallium according to claim 1, it is characterised in that the nano hydrated manganese oxide is inhaled Attached dose of preparation method includes：
Prepare first and contain Manganous sulfate monohydrate MnSO4·H2O, disodium ethylene diamine tetraacetate EDTA-Na2, nitric acid HNO3Just Beginning manganese solution, wherein the MnSO4·H2O concentration is 0.5%~2%, the EDTA-Na2Concentration for 0.1%~ 0.3%, the HNO3Concentration is 2%~4%；
Again into the initial manganese solution add mass concentration be 0~40% cationic ion-exchange resin, and soak reaction 1~ 2h；Wherein described cationic ion-exchange resin includes：D001, D402 or 001 type ion exchange resin；
Then KMnO is added4Solution, generates the nano hydrated manganese oxide sorbents；The KMnO wherein added4Solution is institute State MnSO in initial manganese solution4·H2O
1~1.1 times of amount.
4. the deep treatment method of waste water containing thallium according to claim 1 or 3, it is characterised in that
The operation filtering velocity of the adsorption tower is 7~15m/h.
CN201510106618.0A 2015-03-11 2015-03-11 Advanced treatment method of thallium-containing wastewater Active CN104692561B (en)

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CN105152388A (en) * 2015-07-13 2015-12-16 江苏凯力克钴业股份有限公司 Advanced treatment and recovery method of nickel and cobalt production enterprise extraction raffinate wastewater
CN109437465A (en) * 2018-11-29 2019-03-08 重庆大学 A method of high-concentration industrial waste water containing thallium is removed using Manganese Ferrite
CN113830850B (en) * 2021-11-08 2022-04-12 昆明理工大学 Smelting wastewater deep thallium removal trapping agent and preparation method thereof
CN114682220B (en) * 2022-06-01 2022-08-23 矿冶科技集团有限公司 Selective adsorption material for treating thallium and mercury-containing wastewater, preparation method thereof and method for treating thallium and mercury-containing wastewater by using selective adsorption material

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US6274045B1 (en) * 1995-05-19 2001-08-14 Lawrence Kreisler Method for recovering and separating metals from waste streams
CN101224408A (en) * 2007-10-26 2008-07-23 南京大学 Environment functional material based on nanoparticles hydrated manganese oxide and preparing method thereof
CN102923874B (en) * 2011-08-12 2014-05-28 中国石油化工股份有限公司 Method for processing wastewater containing heavy metal ions
CN104310672B (en) * 2014-10-27 2016-02-24 湖南净源环境工程有限公司 Waste water containing thallium Strong oxdiative coagulation and adsorption recovery process

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