CN105692764B - A kind of lead-zinc smelting wastewater removes thallium method - Google Patents
A kind of lead-zinc smelting wastewater removes thallium method Download PDFInfo
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- CN105692764B CN105692764B CN201610116112.2A CN201610116112A CN105692764B CN 105692764 B CN105692764 B CN 105692764B CN 201610116112 A CN201610116112 A CN 201610116112A CN 105692764 B CN105692764 B CN 105692764B
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Removal Of Specific Substances (AREA)
Abstract
Thallium method is removed the present invention relates to a kind of lead-zinc smelting wastewater, this method comprises the steps of：(1) manganese ore is ground into 200 mesh manganese mineral powder below；(2) manganese mineral powder is added in lead-zinc smelting wastewater the ratio that 1g manganese mineral powders are added in 100~500ml lead-zinc smelting wastewaters, and aeration adjusts pH value to 10 after 1 hour, then is aerated 1 hour, stands 1 hour heel row and puts clear liquid, you can.Not only thallium removal rate is up to up to 99.9% this method, but also is had the advantages that cheap and environmentally friendly.
Description
Technical field
The present invention relates to water-treatment technology fields to concretely relate to more particularly, to the processing of waste water or sewage
Except the method for heavy metal in waste water thallium.
Background technology
Thallium is a kind of dissipated metal element, and toxicity is more than As, Hg, Cd, Pb, and has certain savings.Thallium pollution
Water body is very harmful to common people's health.In view of the toxic of thallium, Environmental Protection Agency has been classified as 13 kinds of preferential prisons
One of heavy metal contaminants of control, China《Heavy metal pollution integrated control " 12th Five-Year Plan " is planned》Also thallium is classified as emphasis prevention and control
One of heavy metal contaminants.
Thallium is normally present in some mineral resources (such as lead zinc sulfide mine).Exist including thallium during mineral resource utilization
Interior heavy metal is released into environment, and the problem of environmental pollution thus caused is on the rise.Pb-Zn deposits smelting industry is thallium environment
The important sources of pollution, thallium cumulative amount is up to 70~80mg/L in the acid waste water that smelting process generates.
Related much to be reported except thallium method has, only State Intellectual Property Office in 2015 discloses serial patent of invention Shen
Please, e.g., " a kind of deep treatment method of waste water containing thallium ", Publication No. CN disclosed in Publication No. CN 104692561A
" a kind of waste water containing thallium process for deeper purifying " disclosed in 104773863A, " one disclosed in Publication No. CN 104803509A
The treatment process and its processing equipment of kind of the heavy metal wastewater thereby containing thallium ", " one kind containing thallium disclosed in Publication No. CN 104925988A
The deep treatment method of equal heavy metal polluted waste waters ", " from the mother of production zinc sulfate disclosed in Publication No. CN 104944623A
The new method of thallium is removed in liquid water and zinc carbonate washings ".The technical characteristics of these patent applications can be summarized as two classes, a kind of
It is that the thallium in waste water is oxidized to trivalent using oxidants such as hydrogen peroxide, potassium permanganate, hypochlorite and persulfates, then exists
It is precipitated and is removed in the form of thallium hydroxide under alkaline condition, another kind of is to use vulcanized sodium sulfides by the thallium in waste water with monovalence
Thallium sulfide form precipitation remove.But these two kinds of methods still have following deficiencies：1, except thallium medicament is chemical reagent, make place
It is higher to manage cost；2, chemical reagent is added and easy tos produce secondary pollution.
Liu Chenmin etc. discloses method [Liu Chenmin, equality, the manganese mud removal that thallium ion in water removal is removed using manganese mud
The research of thallium ion in water, Jilin University's journal (geoscience version) S1 phases in 2015], this method utilizes potassium permanganate and dioxygen
Manganese in manganese mud is converted to monovalence thallium in manganese dioxide adsorption precipitation waste water by water as oxidant, adds adjusting PH with base value heavy to 10
Trivalent thallium in the waste water of shallow lake.But there is also two problems, first, the manganese dioxide absorption monovalence thallium prepared is easy by waste water
The influence of other coexisting ion competitive Adsorptions, the maximum material removal rate of thallium only have 97%；Second is that industry byproduct manganese mud, manganese are main
Exist in the form of inertia Mn oxide, chemical reagent potassium permanganate need to be used to carry out Oxidative activation, however it remains secondary pollution
It is insufficient.
Invention content
Thallium method is removed technical problem to be solved by the invention is to provide a kind of lead-zinc smelting wastewater, this method has warp
Ji and the high advantage of removal rate.
The present invention solve above-mentioned technical problem scheme be：
A kind of lead-zinc smelting wastewater removes thallium method, and this approach includes the following steps：
(1) manganese ore is ground into 200 mesh manganese mineral powder below；
(2) lead-zinc smelting wastewater is added in manganese mineral powder by the ratio that 1g manganese mineral powders are added in 100~500ml lead-zinc smelting wastewaters
In, aeration adjusts pH value to 10 after 1 hour, then is aerated 1 hour, stands 1 hour heel row and puts clear liquid, you can.
The reaction principle of said program is as described below：
(1) manganese mineral powder is added lead-zinc smelting wastewater (waste acid) and dissolves out manganese
Manganese mineral powder+smelting wastewater → Mn2+ ①
(2) it is aerated (O2) and alkaline condition under (pH value is adjusted to 10), first, making the original trivalent thallium of smelting wastewater with Tl
(OH)3Form precipitates, second is that dissolution manganese is made to be converted to MnO2
Smelting wastewater original Tl (III)+OH-→Tl(OH)3↓ ②
Mn2++O2+OH-→MnO2 ③
(3)MnO2In aeration (O2) and alkaline condition under be further oxidized to MnO4 2-(MnO4)
MnO2+O2+OH-→MnO4 2- ④
(4)MnO4 2-With O2Collaboration is fully oxidized at trivalent thallium and with Tl (OH) by monovalence thallium in smelting wastewater3Form is complete
Precipitation
Tl(Ⅰ)+MnO4 2-/O2→Tl(Ⅲ) ⑤
Tl(Ⅲ)+OH-→Tl(OH)3↓ ⑥
Due to MnO4 2-Monovalence thallium is oxidized to thallic while itself is reduced into MnO2, in aeration (O2) and alkaline item
Under part, MnO2It is oxidized to MnO again4 2-, MnO4 2-Actually play catalysed oxidn, therefore the MnO generated4 2-By monovalence thallium
It is very high to be oxidized to thallic efficiency；Again due to Tl (OH)3Very low (Ksp=1.68 × 10 of solubility product constant-44), it will
PH is adjusted to 7, and the concentration for theoretically discharging thallium in the clear liquid on sediment is just reduced to 1.68 × 10-23mol/L。
It is of the present invention that there is following advantageous effect compared with the prior art except thallium method：
1, dexterously utilize manganese ore in manganese mainly in the form of manganese carbonate exist and lead-zinc smelting wastewater highly acidity (pH=
Manganese mineral powder is directly added to the manganese in lead-zinc smelting wastewater in i.e. leachable manganese mineral powder by 0-1) the characteristics of, so as to avoid existing
The shortcomings that thering is technology to be activated using chemical reagent potassium permanganate and causing secondary pollution.
2, in being sufficiently stirred of being aerated twice and under oxidation and pH value will be adjusted to 10, and will on the one hand make waste water original
Trivalent thallium is with Tl (OH)3Form precipitates, and dissolution manganese is on the other hand made to be converted to MnO2It is reoxidised into MnO4, and then makes smelting
Monovalence thallium is fully oxidized at trivalent thallium and with Tl (OH) in waste water3Form precipitates completely.Two aspects integrate, not only lead zinc smelting
The removal rate of thallium is up to 99% or more in refining waste water, but also has the advantages that cheap and environmentally friendly.
Specific implementation mode
The beneficial effect of thallium method is removed below by way of the specific experiment lead-zinc smelting wastewater that comes that the present invention is further explained
Fruit.
Example 1
Manganese ore used comes from Hunan manganese ore in this example, contains manganese 21%；Pb-Zn deposits smelting wastewater used comes from Guangdong smeltery,
Thallium-containing quantity is 78mg/L.
Manganese ore was ground into the miberal powder of 200 mesh, by lead-zinc smelting wastewater=1 mine powder ︰：The ratio of 100 (g/ml) is added
In the lead-zinc smelting wastewater of 1L 78.00mg containing thallium, aeration adjusts pH value to 10, then be aerated 1 hour, gained mixing is molten after 1 hour
Liquid stands 1 hour, discharges the clear liquid on sediment.Use the thallium content in atomic absorption spectrum detection precipitation for 77.84mg, meter
It is 99.8% to calculate thallium removal rate.
Example 2
Manganese ore used comes from Guangxi manganese ore in this example, contains manganese 23%；Pb-Zn deposits smelting wastewater used comes from Guangxi smeltery,
Thallium-containing quantity is 76mg/L.
Manganese ore was ground into the miberal powder of 200 mesh, by lead-zinc smelting wastewater=1 mine powder ︰：The ratio of 200 (g/ml) is added
In the lead-zinc smelting wastewater of 1L 76.00mg containing thallium, aeration adjusts pH value to 10, then be aerated 1 hour, gained mixing is molten after 1 hour
Liquid stands 1 hour, discharges the clear liquid on sediment.Use the thallium content in atomic absorption spectrum detection precipitation for 75.94mg, meter
It is 99.9% to calculate thallium removal rate.
Example 3
Manganese ore used comes from Hunan manganese ore in this example, contains manganese 21%；Pb-Zn deposits smelting wastewater used comes from Hunan smeltery,
Thallium-containing quantity is 72mg/L.
Manganese ore was ground into the miberal powder of 200 mesh, by lead-zinc smelting wastewater=1 mine powder ︰：The ratio of 300 (g/ml) is added
In the lead-zinc smelting wastewater of 1L 72.00mg containing thallium, aeration adjusts pH value to 10, then be aerated 1 hour, gained mixing is molten after 1 hour
Liquid stands 1 hour, discharges the clear liquid on sediment.Use the thallium content in atomic absorption spectrum detection precipitation for 71.87mg, meter
It is 99.8% to calculate thallium removal rate.
Example 4
Manganese ore used comes from Chongqing manganese ore in this example, contains manganese 25%；Pb-Zn deposits smelting wastewater used comes from Guangdong smeltery,
Thallium-containing quantity is 64mg/L.
Manganese ore was ground into the miberal powder of 200 mesh, by lead-zinc smelting wastewater=1 mine powder ︰：The ratio of 400 (g/ml) is added
In the lead-zinc smelting wastewater of 1L 64.00mg containing thallium, aeration adjusts pH value to 10, then be aerated 1 hour, gained mixing is molten after 1 hour
Liquid stands 1 hour, discharges the clear liquid on sediment.Use the thallium content in atomic absorption spectrum detection precipitation for 63.89mg, meter
It is 99.8% to calculate thallium removal rate.
Example 5
Manganese ore used comes from Chongqing manganese ore in this example, contains manganese 25%；Pb-Zn deposits smelting wastewater used comes from Guangxi smeltery,
Thallium-containing quantity is 76mg/L.
Manganese ore was ground into the miberal powder of 200 mesh, by lead-zinc smelting wastewater=1 mine powder ︰：The ratio of 500 (g/ml) is added
In the lead-zinc smelting wastewater of 1L 76.00mg containing thallium, aeration adjusts pH value to 10, then be aerated 1 hour, gained mixing is molten after 1 hour
Liquid stands 1 hour, discharges the clear liquid on sediment.Use the thallium content in atomic absorption spectrum detection precipitation for 75.54mg, meter
It is 99.4% to calculate thallium removal rate.
Example 6
Manganese ore used comes from Guangxi manganese ore in this example, contains manganese 23%；Pb-Zn deposits smelting wastewater used comes from Hunan smeltery,
Thallium-containing quantity is 72mg/L.
Manganese ore was ground into the miberal powder of 200 mesh, by lead-zinc smelting wastewater=1 mine powder ︰：The ratio of 500 (g/ml) is added
In the lead-zinc smelting wastewater of 1L 72.00mg containing thallium, aeration adjusts pH value to 10, then be aerated 1 hour, gained mixing is molten after 1 hour
Liquid stands 1 hour, discharges the clear liquid on sediment.Use the thallium content in atomic absorption spectrum detection precipitation for 71.60mg, meter
It is 99.4% to calculate thallium removal rate.
Claims (1)
1. a kind of lead-zinc smelting wastewater removes thallium method, this method comprises the steps of：
(1) manganese ore is ground into 200 mesh manganese mineral powder below；
(2) manganese mineral powder is added in lead-zinc smelting wastewater the ratio that 1g manganese mineral powders are added in 100~500ml lead-zinc smelting wastewaters,
Aeration adjusts pH value to 10 after 1 hour, then is aerated 1 hour, stands 1 hour heel row and puts clear liquid, you can.
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| CN108083505A (en) * | 2017-12-28 | 2018-05-29 | 吉林建筑大学 | A kind of method for removing thallium in water removal using single persulfate reinforcing manganese sand |
| CN108298658B (en) * | 2018-03-09 | 2019-06-28 | 广东省矿产应用研究所 | Lead-zinc smelting wastewater deep thallium removal trapping agent and application thereof |
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