CN113264603A - Method for treating acid wastewater with high arsenic and thallium contents in sulfuric acid - Google Patents
Method for treating acid wastewater with high arsenic and thallium contents in sulfuric acid Download PDFInfo
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F2305/00—Use of specific compounds during water treatment
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- C02F2305/026—Fenton's reagent
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Abstract
The invention provides a method for treating high-arsenic thallium-sulfate acidic wastewater, which comprises the following steps: adding limestone into sewage for neutralization, feeding the sewage into a first-stage thickener, performing underflow filter pressing to obtain first-stage neutralized slag, adding penetrating water into clear liquid, feeding the clear liquid into a second-stage oxidation reaction, performing second-stage neutralization, feeding the clear liquid into a second-stage thickener, performing underflow filter pressing to obtain second-stage neutralized slag, feeding the clear liquid into a third-stage pH adjusting tank, a third-stage first-stage neutralizing tank, a third-stage oxidation tank and a third-stage second-stage neutralizing tank in sequence into a third-stage thickener, performing underflow filter pressing to obtain third-stage neutralized slag, feeding the clear liquid into a fourth-stage vulcanization tank 1 and a fourth-stage vulcanization tank 2 in sequence, feeding the clear liquid into a fourth-stage thickener, performing underflow filter pressing to obtain fourth-stage slag, and feeding the clear liquid into a pressurized water tank for recycling. The method has strong application operability, strong continuity of the process flow, sectional treatment and simple operation, and is suitable for treating the polluted acid (wastewater) containing arsenic and thallium.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for treating high-arsenic and high-thallium acid wastewater of sulfuric acid.
Background
The prior method for treating the acid wastewater with high arsenic and thallium content by sulfuric acid adopts a lime neutralization method to increase the pH value to more than 12 at one time, accelerates the reaction by compressed air in a thickener, pumps the reaction to a filter press for filter pressing, overflows filtrate to an electrochemical procedure for advanced treatment after passing through a three-stage neutralization tank, and has unstable effect after the pretreatment procedure, particularly arsenic and thallium exceed the water inlet requirement of the electrochemical procedure at times, thereby further increasing the treatment cost. In addition, the sulfuric acid wastewater is also subjected to secondary vulcanization and secondary neutralization, the arsenic removal effect of the method is obvious, the thallium removal effect is general, especially under the condition of high source thallium, so that the full-element treatment can reach the standard by often using the cooperation of an electrochemical or biological agent thallium removal technology, and the patented agent is also a factor for increasing the treatment cost.
The most prominent defect of the existing lime neutralization pretreatment and electrochemical advanced treatment method in lead smelteries is that it is difficult to stably realize that all arsenic, cadmium, thallium, lead, zinc, mercury and fluorine reach the emission standard of lead and zinc industrial pollutants (GB25466-2010), particularly, the arsenic removal and thallium removal capability of the pretreatment process is limited, and the source belongs to high-arsenic and high-thallium wastewater, so the burden of electrochemical advanced treatment is increased, the consumption of polar plates and the consumption of thallium removal agents are increased, and the cost is increased.
Disclosure of Invention
The invention aims to provide a method for treating high-arsenic and thallium sulfate acidic wastewater, which is improved in a pretreatment process aiming at the problems of unstable sulfuric acid acidic wastewater treatment effect and high treatment cost of the existing lead smelting plant and aims at achieving good sulfuric acid acidic wastewater treatment effect and reducing cost by adopting a four-stage process treatment method.
The technical scheme of the invention is realized as follows:
the invention provides a method for treating high-arsenic thallium-sulfate acidic wastewater, which comprises the following steps: adding limestone into sewage for neutralization, feeding the sewage into a first-stage thickener, performing underflow filter pressing to obtain first-stage neutralized slag, adding penetrating water into clear liquid, feeding the clear liquid into a second-stage oxidation reaction, performing second-stage neutralization, feeding the clear liquid into a second-stage thickener, performing underflow filter pressing to obtain second-stage neutralized slag, feeding the clear liquid into a third-stage pH adjusting tank, a third-stage first-stage neutralizing tank, a third-stage oxidation tank and a third-stage second-stage neutralizing tank in sequence into a third-stage thickener, performing underflow filter pressing to obtain third-stage neutralized slag, feeding the clear liquid into a fourth-stage vulcanization tank 1 and a fourth-stage vulcanization tank 2 in sequence, feeding the clear liquid into a fourth-stage thickener, performing underflow filter pressing to obtain fourth-stage slag, and feeding the clear liquid into a pressurized water tank for recycling.
Firstly, a step of: and adjusting the pH value of the calcium carbonate slurry, and controlling the pH value end point to be 2-3.
A second step: the pH value of the lime milk is adjusted, the pH value end point is controlled to be 11.5-12, the potential is controlled to be +550mv, and meanwhile, arsenic is removed by Fenton medicaments (hydrogen peroxide and ferric salt).
Third step: and (3) after the pH value of the sulfuric acid is adjusted back to 3-6, adjusting the pH value by using lime milk, controlling the pH value end point to be 6-8 and the potential to be +650mv, and deeply removing arsenic by using Fenton medicaments (hydrogen peroxide and iron salt).
Fourthly, four steps: adjusting the pH value of the lime milk, controlling the pH value end point to be 11.5-12, achieving the effect of deeply removing thallium through sodium sulfide and portland cement, and controlling the potential to be-300 mv.
As a further improvement of the invention, the control condition for limestone neutralization is a pH endpoint of 2.
As a further improvement of the invention, 2kg/m of hydrogen peroxide is added in the secondary oxidation reaction3And iron salt 1kg/m3。
As a further improvement of the invention, lime milk is respectively added into the first-stage neutralization and the second-stage neutralization of the second stage and the second stage, and the time is respectively 30-40 min.
As a further improvement of the invention, after two-stage secondary neutralization, the pH of the liquid is 11.5-12.
As a further improvement of the invention, the three-stage pH adjusting tank is a sulfuric acid solution with the pH value of 3-6.
As a further improvement of the invention, 1kg/m of hydrogen peroxide is added into the three-stage oxidation tank3And iron salt 1kg/m3。
As a further improvement of the invention, lime milk or sulfuric acid is added into the three-stage and two-stage neutralization tank to adjust the pH value to 6-7.
As a further improvement of the invention, lime is added into the four-stage vulcanization tank 1 to adjust the pH value to 11.5-12, and Na is added2The S solution is added in an amount of 0.3-0.4kg/m3。
As a further improvement of the invention, silicate slurry is added into the four-stage vulcanizing tank 2, and the adding amount is 0.5-1kg/m3。
The invention has the following beneficial effects: the invention relates to a method for treating acid wastewater with high arsenic and thallium contents in sulfuric acid. The invention aims to mainly solve the problem that the acid wastewater generated by a sulfuric acid system of a lead smelting plant is about 200 tons per day, the wastewater has complex components and contains elements such as arsenic, cadmium, thallium, lead, zinc, mercury, fluorine and the like, wherein the content of arsenic and thallium is high, the conventional treatment method adopts a lime neutralization pretreatment and electrochemical advanced treatment method, the treatment effect of the method is unstable, particularly the arsenic and thallium are difficult to stabilize for a long time, the cost is high, the improved method stably realizes that all of arsenic, cadmium, thallium, lead, zinc, mercury and fluorine reach the discharge standard of lead and zinc industrial pollutants (GB25466-2010), and the cost is greatly reduced by taking an electrochemical process as a security system.
The method has strong application operability, strong continuity of process flow, sectional treatment, easy control of workers and simple and clear operation, is suitable for treating the waste acid (wastewater) with high arsenic and thallium content, can treat 200 tons of waste acid or wastewater every day, and provides powerful guarantee for lead smelting production.
The method realizes the standard reaching of all heavy metal elements through conventional medicament treatment, cancels advanced treatment processes such as biological agents, electrochemistry and the like, breaks through monopoly of environment-friendly medicaments with special patent properties of environment-friendly companies, can treat high thallium waste acid and realize the stability of thallium indexes better compared with the traditional medicament treatment method of firstly vulcanizing and then neutralizing, and has the cost aspect which is 25-35 yuan/ton lower than that of the method for realizing the standard reaching of all heavy metal elements in the same industry.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram of the treatment method of the sulfuric acid high arsenic and thallium acidic wastewater.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to the attached figure 1, the method for treating the sulfuric acid high-arsenic thallium acidic wastewater comprises the following steps:
adding limestone into sewage for neutralization under the condition that the pH end point is 2, feeding the sewage into a first-stage thickener, performing underflow filter pressing to obtain first-stage neutralized slag, adding penetrating water into clear liquid, feeding the clear liquid into a second-stage oxidation reaction, and adding 2kg/m hydrogen peroxide3And iron salt 1kg/m3Then, after two-stage and two-stage neutralization, lime cream is added into the first-stage and two-stage neutralization respectively and aeration treatment is carried out for 30min, after neutralization, the pH of the liquid is 11.5, the liquid enters a two-stage thickener, underflow filter pressing is carried out to obtain second-stage neutralization slag, clear liquid sequentially enters a three-stage pH adjusting tank, sulfuric acid solution with the pH of 3 is contained in the three-stage pH adjusting tank, and a three-stage first-stage neutralization tank and a three-stage oxidation tank (1 kg/m hydrogen peroxide is added) are respectively added3And iron salt 1kg/m3) The three-stage two-stage neutralization tank (lime milk or sulfuric acid is added to adjust the pH value to be 6) enters a three-stage thickener, underflow filter pressing is carried out to obtain three-stage neutralization slag, and clear liquid sequentially enters a four-stage vulcanization tank 1 (lime is added to adjust the pH value to be 11.5, and Na is added to adjust the pH value to be 11.5)2The S solution is added in an amount of 0.3kg/m3) And a four-stage vulcanizing tank 2 (adding silicate slurry with the addition amount of 0.5 kg/m)3) Then the obtained product is fed into a four-stage thickener, the underflow is filter-pressed to obtain four-stage slag, and the clear liquid is fed into a pressurized water tank for recycling.
Example 2
Referring to the attached figure 1, the method for treating the sulfuric acid high-arsenic thallium acidic wastewater comprises the following steps:
adding limestone into sewage for neutralization under the condition that the pH end point is 2, feeding the sewage into a first-stage thickener, performing underflow filter pressing to obtain first-stage neutralized slag, adding penetrating water into clear liquid, feeding the clear liquid into a second-stage oxidation reaction, and adding 2kg/m hydrogen peroxide3And iron salt 1kg/m3Then, after two-stage and two-stage neutralization, lime cream is added into the first-stage and two-stage neutralization respectively and aeration treatment is carried out for 40min, after neutralization, the pH of the liquid is 12, the liquid enters a two-stage thickener, underflow filter pressing is carried out to obtain second-stage neutralization slag, clear liquid sequentially enters a three-stage pH adjusting tank, sulfuric acid solution with the pH of 6 is arranged in the three-stage pH adjusting tank, and a three-stage first-stage neutralization tank and a three-stage oxidation tank (1 kg/m hydrogen peroxide is added) are respectively carried out3And iron salt 1kg/m3) The three-stage two-stage neutralization tank (adding lime milk or sulfuric acid to adjust pH to 6-7) enters a three-stage thickener, underflow filter pressing is carried out to obtain three-stage neutralization slag, and clear liquid sequentially enters a four-stage vulcanization tank 1 (adding lime to adjust pH to 12 and adding Na2The S solution is added in an amount of 0.4kg/m3) And a four-stage vulcanizing tank 2 (adding silicate slurry with the addition amount of 1 kg/m)3) Then the obtained product is fed into a four-stage thickener, the underflow is filter-pressed to obtain four-stage slag, and the clear liquid is fed into a pressurized water tank for recycling.
Example 3
Referring to the attached figure 1, the method for treating the sulfuric acid high-arsenic thallium acidic wastewater comprises the following steps:
adding limestone into sewage for neutralization under the condition that the pH end point is 2, feeding the sewage into a first-stage thickener, performing underflow filter pressing to obtain first-stage neutralized slag, adding penetrating water into clear liquid, feeding the clear liquid into a second-stage oxidation reaction, and adding 2kg/m hydrogen peroxide3And iron salt 1kg/m3Then, after two-stage and two-stage neutralization, lime cream is added into the first-stage and two-stage neutralization respectively and aeration treatment is carried out for 30-40min, after neutralization, the pH of the liquid is 11.7, the liquid enters a two-stage thickener, underflow filter pressing is carried out to obtain second-stage neutralization slag, clear liquid sequentially enters a three-stage pH adjusting tank, sulfuric acid solution with the pH of 4.5 is filled in the three-stage pH adjusting tank, and a three-stage first-stage neutralization tank and a three-stage oxidation tank (1 kg/m hydrogen peroxide is added) are respectively carried out3And iron salt 1kg/m3) The three-stage two-stage neutralization tank (adding lime milk or sulfuric acid to adjust pH to 6.5) enters a three-stage thickener, underflow filter pressing is carried out to obtain three-stage neutralization slag, and clear liquid sequentially enters a four-stage vulcanization tank 1 (adding lime to adjust pH to 11.7 and adding Na2The S solution is added in an amount of 0.35kg/m3) And a four-stage vulcanizing tank 2 (adding silicate slurry with the addition amount of 0.7 kg/m)3) Then, go intoFeeding into a four-section thickener, performing filter pressing on the bottom flow to obtain four-section slag, and feeding the clear liquid into a pressurized water tank for recycling.
Test example 1
The contents of arsenic and thallium in the raw sewage and the water purified by the methods of examples 1 to 3 were measured. The results are shown in Table 1.
TABLE 1
| Group of | Arsenic element (mg/L) | Thallium element (ug/L) |
| Raw water | 2575 | 2531 |
| Example 1 | 0.15 | 2.91 |
| Example 2 | 0.11 | 2.23 |
| Example 3 | 0.09 | 2.54 |
As can be seen from the above table, the content of the pollutants in the sewage treated by the method of the invention is obviously reduced, and the sewage meets the requirements of national standards.
Compared with the prior art, the invention relates to a method for treating acid wastewater with high arsenic and thallium content in sulfuric acid. The invention aims to mainly solve the problem that the acid wastewater generated by a sulfuric acid system of a lead smelting plant is about 200 tons per day, the wastewater has complex components and contains elements such as arsenic, cadmium, thallium, lead, zinc, mercury, fluorine and the like, wherein the content of arsenic and thallium is high, the conventional treatment method adopts a lime neutralization pretreatment and electrochemical advanced treatment method, the treatment effect of the method is unstable, particularly the arsenic and thallium are difficult to stabilize for a long time, the cost is high, the improved method stably realizes that all of arsenic, cadmium, thallium, lead, zinc, mercury and fluorine reach the discharge standard of lead and zinc industrial pollutants (GB25466-2010), and the cost is greatly reduced by taking an electrochemical process as a security system.
The method has strong application operability, strong continuity of process flow, sectional treatment, easy control of workers and simple and clear operation, is suitable for treating the waste acid (wastewater) with high arsenic and thallium content, can treat 200 tons of waste acid or wastewater every day, and provides powerful guarantee for lead smelting production.
The method realizes the standard reaching of all heavy metal elements through conventional medicament treatment, cancels advanced treatment processes such as biological agents, electrochemistry and the like, breaks through monopoly of environment-friendly medicaments with special patent properties of environment-friendly companies, can treat high thallium waste acid and realize the stability of thallium indexes better compared with the traditional medicament treatment method of firstly vulcanizing and then neutralizing, and has the cost aspect which is 25-35 yuan/ton lower than that of the method for realizing the standard reaching of all heavy metal elements in the same industry.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for treating high-arsenic thallium sulfate acidic wastewater is characterized by comprising the following steps: adding limestone into sewage for neutralization, feeding the sewage into a first-stage thickener, performing underflow filter pressing to obtain first-stage neutralized slag, adding penetrating water into clear liquid, feeding the clear liquid into a second-stage oxidation reaction, performing second-stage neutralization, feeding the clear liquid into a second-stage thickener, performing underflow filter pressing to obtain second-stage neutralized slag, feeding the clear liquid into a third-stage pH adjusting tank, a third-stage first-stage neutralizing tank, a third-stage oxidation tank and a third-stage second-stage neutralizing tank in sequence into a third-stage thickener, performing underflow filter pressing to obtain third-stage neutralized slag, feeding the clear liquid into a fourth-stage vulcanization tank 1 and a fourth-stage vulcanization tank 2 in sequence, feeding the clear liquid into a fourth-stage thickener, performing underflow filter pressing to obtain fourth-stage slag, and feeding the clear liquid into a pressurized water tank for recycling.
2. The method for treating high arsenic and thallium sulfate acidic wastewater as recited in claim 1, wherein the control condition for limestone neutralization is a pH endpoint of 2.
3. The method for treating high-arsenic thallium sulfate acidic wastewater as claimed in claim 1, wherein 2kg/m hydrogen peroxide is added in the secondary oxidation reaction3And iron salt 1kg/m3。
4. The method for treating high arsenic and thallium sulfate acidic wastewater as recited in claim 1, wherein lime milk is added into the second stage first-stage neutralization and the second stage second-stage neutralization respectively and the aeration treatment is carried out for 30-40 min.
5. The method for treating high arsenic and thallium sulfate acidic wastewater as recited in claim 1, wherein after the two-stage secondary neutralization, the pH of the liquid is 11.5-12.
6. The method for treating high-arsenic thallium sulfate acidic wastewater as recited in claim 1, wherein a sulfuric acid solution having a pH of 3-6 is provided in the three-stage pH adjustment tank.
7. The method for treating high-arsenic thallium sulfate acidic wastewater as claimed in claim 1, wherein 1kg/m hydrogen peroxide solution is added into the tri-stage oxidation tank3And iron salt 1kg/m3。
8. The method for treating high-arsenic thallium acid wastewater sulfate according to claim 1, wherein lime milk or sulfuric acid is added to the three-stage and two-stage neutralization tank to adjust the pH value to 6-7.
9. The method for treating high arsenic and thallium sulfate acidic wastewater as claimed in claim 1, wherein lime is added to the four-stage sulfidizing tank 1 to adjust pH to 11.5-12, and Na is added2The S solution is added in an amount of 0.3-0.4kg/m3。
10. The method for treating high arsenic and thallium sulfate acidic wastewater as claimed in claim 1, wherein silicate slurry is added to the four-stage vulcanization tank 2 in an amount of 0.5-1kg/m3。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180748A (en) * | 2022-08-23 | 2022-10-14 | 水口山有色金属有限责任公司 | Waste acid treatment method |
| CN115432854A (en) * | 2022-09-06 | 2022-12-06 | 水口山有色金属有限责任公司 | Method for preferentially enriching and removing thallium from high-halogen waste acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109110981A (en) * | 2018-11-05 | 2019-01-01 | 湖南水口山有色金属集团有限公司 | A method of removing thallium in high acid water containing halogen |
| CN111635033A (en) * | 2020-06-05 | 2020-09-08 | 中国恩菲工程技术有限公司 | Method and device for treating thallium and arsenic-containing waste acid |
-
2020
- 2020-10-27 CN CN202011160982.2A patent/CN113264603A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109110981A (en) * | 2018-11-05 | 2019-01-01 | 湖南水口山有色金属集团有限公司 | A method of removing thallium in high acid water containing halogen |
| CN111635033A (en) * | 2020-06-05 | 2020-09-08 | 中国恩菲工程技术有限公司 | Method and device for treating thallium and arsenic-containing waste acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180748A (en) * | 2022-08-23 | 2022-10-14 | 水口山有色金属有限责任公司 | Waste acid treatment method |
| CN115432854A (en) * | 2022-09-06 | 2022-12-06 | 水口山有色金属有限责任公司 | Method for preferentially enriching and removing thallium from high-halogen waste acid |
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