CN113387472A - Method for removing cadmium and thallium from indium-containing wastewater - Google Patents
Method for removing cadmium and thallium from indium-containing wastewater Download PDFInfo
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- CN113387472A CN113387472A CN202110634465.2A CN202110634465A CN113387472A CN 113387472 A CN113387472 A CN 113387472A CN 202110634465 A CN202110634465 A CN 202110634465A CN 113387472 A CN113387472 A CN 113387472A
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- indium
- thallium
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- 239000002351 wastewater Substances 0.000 title claims abstract description 68
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 62
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 49
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 48
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000011085 pressure filtration Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 abstract description 4
- 150000004679 hydroxides Chemical class 0.000 abstract description 4
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 5
- -1 thallium ions Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- 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
-
- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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)
Abstract
The invention discloses a method for removing cadmium and thallium from indium-containing wastewater, and belongs to the field of hydrometallurgy. The method for removing cadmium and thallium from the indium-containing wastewater adopts a distributed precipitation method to precipitate and filter out indium elements in the indium-containing wastewater, and then adjusts the pH value of the solution to a specific alkaline value to precipitate and remove cadmium and thallium by forming hydroxides; and after the precipitation treatment, twice circulating filter pressing treatment is adopted to ensure the removal efficiency of target ions in the wastewater during two-stage treatment, compared with the traditional method using an MVR evaporation step in the whole process, the cost is lower, the operation efficiency is higher, the content of cadmium and thallium in the treated wastewater is obviously reduced, and the heavy metal pollution degree of the wastewater is reduced.
Description
Technical Field
The invention relates to the field of hydrometallurgy, in particular to a method for removing cadmium and thallium from indium-containing wastewater.
Background
A large amount of high-purity indium (more than 99.99 percent) metal is needed in the preparation and use processes of Indium Tin Oxide (ITO) targets or indium-containing targets, and the high-purity indium is mainly prepared by extracting crude indium by a wet method and then electrolytically refining and purifying the crude indium at present. However, this method produces a large amount of waste water during the wet extraction process, and the waste water contains a large amount of impurities (mainly cadmium ions and thallium ions), which makes the rear end of the waste water difficult to handle. The conventional scheme is to use an MVR evaporator to evaporate and treat wastewater, however, the cost of wastewater treatment is high, large-scale industrial development and planning are not facilitated, and some simpler treatment means in the prior art are difficult to remove impurities such as cadmium thallium ions to the desired concentration.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide the method for removing cadmium and thallium from the indium-containing wastewater, and compared with the traditional MVR evaporation method, the method has the advantages of simple operation steps, lower cost, high impurity removal efficiency, effective reduction of the heavy metal ion content of the wastewater and reduction of the pollution degree of the wastewater.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for removing cadmium and thallium from indium-containing wastewater comprises the following steps:
(1) adjusting the pH value of the indium-containing wastewater to acidity to precipitate indium in the wastewater, then performing primary circulating pressure filtration treatment on the precipitated wastewater, and testing the indium content in the solution, wherein the solution to be treated is in a clear state;
(2) if the indium content in the solution is less than or equal to 1ppm, obtaining filtered water A; if the indium content in the solution is more than 1ppm, the pressure filtration treatment is continuously and circularly repeated until the indium content reaches the standard;
(3) and adjusting the pH of the filtered water A to 8-10, and then carrying out secondary circulating filter pressing treatment, wherein the solution to be treated is in a clear state, so that the treated wastewater after cadmium and thallium are removed is obtained.
In the method for removing cadmium and thallium from the indium-containing wastewater, a distributed precipitation method is adopted, firstly, indium elements in the indium-containing wastewater are precipitated to form a precipitate, the precipitate is filtered, and then, the pH value of the solution is adjusted to a specific value, and cadmium and thallium are precipitated and removed in the form of hydroxide; and after precipitation, twice circulating filter pressing treatment is adopted to ensure the removal efficiency of target ions in the wastewater during two-stage treatment, compared with the traditional step of using an MVR evaporation method in the whole process, the cost is lower, the operation efficiency is higher, the content of cadmium and thallium in the treated wastewater is obviously reduced, and the heavy metal pollution degree of the wastewater is reduced.
Preferably, the indium content of the indium-containing wastewater in the step (1) is less than or equal to 2g/L, and the total content of cadmium and thallium is 20-50 ppm.
Preferably, the pH of the indium-containing wastewater obtained in the step (1) is adjusted to be 4-5 when the wastewater is acidic.
After hydrogen ions with specific concentration are added into the wastewater, indium ions can be completely precipitated, and the high efficiency of subsequent circulating filter pressing is ensured.
Preferably, the temperature in the primary circulating pressure filtration treatment in the step (1) is controlled to be 25-35 ℃, and the pressure filtration pressure is 0.5-0.7 MPa.
Through specific temperature and pressure regulation, the circulating filter pressing treatment consumes shorter time, and the indium content in the obtained filtrate meets the wastewater discharge standard.
Preferably, a precipitating aid is added when the pH of the filtered water A in the step (2) is adjusted to 8-10;
more preferably, the co-precipitant is sodium sulfide.
Heavy metal ions cadmium and thallium in the wastewater and sulfides corresponding to the heavy metal ions cadmium and thallium are both insoluble precipitates, the solubility of the heavy metal ions cadmium and thallium is lower than that of hydroxides, and in the process of adjusting alkalinity to precipitate the heavy metal ions by the hydroxides, a certain amount of sodium sulfide is added to enable the sulfide precipitates and the hydroxide precipitates to be generated simultaneously, so that the removal efficiency is improved, and excessive treatment cost cannot be increased.
Preferably, the temperature in the secondary circulating filter pressing treatment in the step (2) is controlled to be 25-35 ℃, the filter pressing pressure is 0.5-0.7 MPa, and the time is 7.5-8.5 h.
After the circulating pressure filtration treatment under the preferable conditions, the concentration of cadmium and thallium ions in the wastewater can be effectively reduced to the minimum, and the removal effect is improved.
The invention has the beneficial effects that: the invention provides a method for removing cadmium and thallium from indium-containing wastewater, which comprises the steps of adopting a distributed precipitation method to precipitate and filter indium elements in the indium-containing wastewater, then adjusting the pH value of a solution to a specific alkaline value to precipitate and remove cadmium and thallium by forming hydroxides; and after the precipitation treatment, twice circulating filter pressing treatment is adopted to ensure the removal efficiency of target ions in the wastewater during two-stage treatment, compared with the traditional step of using an MVR evaporation method in the whole process, the cost is lower, the operation efficiency is higher, the content of cadmium and thallium in the treated wastewater is obviously reduced, the content of cadmium and thallium is only about 0.1ppm, and the heavy metal pollution degree of the wastewater is reduced.
Drawings
FIG. 1 is a schematic flow chart of the method for removing cadmium and thallium from indium-containing wastewater according to the invention.
Detailed Description
For better illustrating the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples, which are intended to be understood in detail, but not intended to limit the present invention.
Example 1
The method for removing cadmium and thallium from indium-containing wastewater disclosed by the invention comprises the following steps of:
(1) adjusting the pH value of 1 ton of indium-containing wastewater (the indium content is 1.2g/L, the cadmium content is 15ppm, and the thallium content is 30ppm) to 4.5 to precipitate indium in the wastewater, and performing one-time circulating pressure filtration treatment until the solution is clear and the indium content is less than or equal to 1ppm to obtain filtered water A; the temperature during the primary circulating filter pressing treatment is controlled to be 25-35 ℃, and the filter pressing pressure is 0.5-0.7 MPa;
(2) adjusting the pH of the filtered water A to 9, adding a small amount of sodium sulfide, and performing secondary circulating filter pressing treatment until the solution is clear, thereby obtaining the treated wastewater after cadmium and thallium are removed; the temperature during the secondary circulating filter pressing treatment is controlled to be 25-35 ℃, and the filter pressing pressure is 0.5-0.7 MPa.
The cadmium content in the treated wastewater after removing the cadmium and the thallium is 0.15ppm, and the thallium content is 0.1 ppm.
Example 2
The method for removing cadmium and thallium from indium-containing wastewater disclosed by the invention comprises the following steps of:
(1) adjusting the pH value of 0.5 ton of indium-containing wastewater (the indium content is 1.8g/L, the cadmium content is 20ppm, and the thallium content is 20ppm) to 5 to precipitate indium in the wastewater, and performing one-time circulating pressure filtration treatment until the solution is clear and the indium content is less than or equal to 1ppm to obtain filtered water A; the temperature during the primary circulating filter pressing treatment is controlled to be 25-35 ℃, and the filter pressing pressure is 0.5-0.7 MPa;
(2) adjusting the pH of the filtered water A to 10, adding a small amount of sodium sulfide, and performing secondary circulating filter pressing treatment until the solution is clear, thereby obtaining the treated wastewater after cadmium and thallium are removed; the temperature during the secondary circulating filter pressing treatment is controlled to be 25-35 ℃, and the filter pressing pressure is 0.5-0.7 MPa.
The cadmium content in the treated wastewater after removing the cadmium and the thallium is 0.1ppm, and the thallium content is 0.1 ppm.
Example 3
The method for removing cadmium and thallium from indium-containing wastewater disclosed by the invention comprises the following steps of:
(1) adjusting the pH value of 1 ton of indium-containing wastewater (the indium content is 1g/L, the cadmium content is 30ppm, and the thallium content is 20ppm) to 4 to precipitate indium in the wastewater, and performing once circulating pressure filtration treatment until the solution is clear and the indium content is less than or equal to 1ppm to obtain filtered water A; the temperature during the primary circulating filter pressing treatment is controlled to be 25-35 ℃, and the filter pressing pressure is 0.5-0.7 MPa;
(2) adjusting the pH of the filtered water A to 8, adding a small amount of sodium sulfide, and performing secondary circulating filter pressing treatment until the solution is clear, thereby obtaining the treated wastewater after cadmium and thallium are removed; the temperature during the secondary circulating filter pressing treatment is controlled to be 25-35 ℃, and the filter pressing pressure is 0.5-0.7 MPa.
The cadmium content in the treated wastewater after removing the cadmium and the thallium is 0.2ppm, and the thallium content is 0.1 ppm.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A method for removing cadmium and thallium from indium-containing wastewater is characterized by comprising the following steps:
(1) adjusting the pH value of the indium-containing wastewater to acidity to precipitate indium in the wastewater, then performing primary circulating pressure filtration treatment on the precipitated wastewater, and testing the indium content in the solution, wherein the solution to be treated is in a clear state;
(2) if the indium content in the solution is less than or equal to 1ppm, obtaining filtered water A; if the indium content in the solution is more than 1ppm, the pressure filtration treatment is continuously and circularly repeated until the indium content reaches the standard;
(3) and adjusting the pH of the filtered water A to 8-10, and then carrying out secondary circulating filter pressing treatment, wherein the solution to be treated is in a clear state, so that the treated wastewater after cadmium and thallium are removed is obtained.
2. The method for removing cadmium and thallium from indium-containing wastewater as claimed in claim 1, wherein the indium content of the indium-containing wastewater in the step (1) is less than or equal to 2g/L, and the total content of cadmium and thallium is 20-50 ppm.
3. The method for removing cadmium and thallium from indium-containing wastewater as claimed in claim 1, wherein the pH of the indium-containing wastewater in step (1) is adjusted to be 4-5 when the wastewater is acidic.
4. The method for removing cadmium and thallium from indium-containing wastewater as claimed in claim 1, wherein the temperature in the primary circulation pressure filtration treatment in step (1) is controlled to be 25 to 35 ℃, and the pressure filtration pressure is 0.5 to 0.7 MPa.
5. The method for removing cadmium and thallium from indium-containing wastewater as claimed in claim 1, wherein a precipitating aid is further added when the pH of the filtrate A in step (2) is adjusted to 8-10.
6. The method for removing cadmium and thallium from indium-containing wastewater of claim 5 wherein the co-precipitant is sodium sulfide.
7. The method for removing cadmium and thallium from indium-containing wastewater as claimed in claim 1, wherein the temperature during the secondary circulation pressure filtration treatment in step (2) is controlled to be 25-35 ℃, the pressure filtration pressure is 0.5-0.7 MPa, and the time is 7.5-8.5 h.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114525403A (en) * | 2022-01-28 | 2022-05-24 | 云锡文山锌铟冶炼有限公司 | Method for removing thallium from indium-containing scum |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114525403A (en) * | 2022-01-28 | 2022-05-24 | 云锡文山锌铟冶炼有限公司 | Method for removing thallium from indium-containing scum |
CN114525403B (en) * | 2022-01-28 | 2023-09-22 | 云锡文山锌铟冶炼有限公司 | Method for removing thallium in indium-containing dross |
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