CN110255770B - Method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag - Google Patents
Method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag Download PDFInfo
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- CN110255770B CN110255770B CN201910592560.3A CN201910592560A CN110255770B CN 110255770 B CN110255770 B CN 110255770B CN 201910592560 A CN201910592560 A CN 201910592560A CN 110255770 B CN110255770 B CN 110255770B
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- 239000002893 slag Substances 0.000 title claims abstract description 93
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 51
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052935 jarosite Inorganic materials 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 239000002253 acid Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000003723 Smelting Methods 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010802 sludge Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011112 process operation Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000002386 leaching Methods 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 231100000820 toxicity test Toxicity 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052844 willemite Inorganic materials 0.000 description 1
Classifications
-
- 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
- C02F1/72—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
- C02F2101/103—Arsenic compounds
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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)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag, belonging to the technical field of heavy metal pollution treatment. The invention mixes the jarosite slag and the carbide slag evenly, and ball-mills the mixture until the granularity of the mixture is not higher than 0.56 μm to obtain mixed slag powder; adding the mixed slag powder and potassium permanganate into the waste acid, uniformly mixing, continuously introducing air under the stirring condition, and performing oxidation dearsenification reaction for 24-36 hours to obtain a solid-liquid mixture; solid-liquid separation is carried out on the solid-liquid mixture to obtain arsenic-containing solid and filtrate, the arsenic-containing solid is stockpiled and treated, and the filtrate is subjected to the next step of deep arsenic removal treatment. The method adopts the jarosite slag and the carbide slag to remove arsenic in the waste acid, has excellent arsenic removal effect, simple process operation and low production cost, generates less sludge after arsenic removal, and relieves the problem of large sludge stockpiling amount.
Description
Technical Field
The invention relates to a method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag, belonging to the technical field of heavy metal pollution treatment.
Background
The jarosite process was developed after years of experimental studies in the resiliant zinc plant of australian zinc electronics, sixty years and is widely used in zinc smelting. China is a big country for zinc production and consumption, over 50 percent of zinc smelting plants adopt jarosite method to remove iron, the method can generate a large amount of jarosite slag in the process of smelting zinc, and the annual slag yield is about half of the zinc yield. These wastes are generally directly stockpiled and cannot be properly handled, causing great harm to the surrounding environment. The jarosite slag mainly contains Fe, S and Zn, and also contains As, Cd, Ga, In and other elements, and the Fe content is generally about 20-30%. The main phase of the jarosite slag is KFe3(SO4)2(OH)6，ZnFe2O4，Zn2SiO4. As a world zinc-producing nation in China, although the annual emission of jarosite slag is great, the utilization rate is very low.
The carbide slag is a byproduct of the hydrolysis reaction of the calcium carbide in the process of preparing the acetylene by the calcium carbide method. The carbide slag mainly comprises Ca (OH)2The other components are derived from impurities brought by lime and coke, mainly oxides of Si, Al, Fe and Mg, and if the impurities are carbide slag discharged from chlor-alkali chemical production plants, the contents of chlorine and alkali are often higher.
The method is widely applied to the treatment method of the polluted acid at present, namely a sulfuration method-a limemite method, and although the method has simple process and low treatment cost, the method has incomplete harmless treatment in practical application and large secondary hazardous waste residue amount. A large amount of waste residues which are difficult to treat and pile are stored in the environment, so that toxic elements are easy to release to pollute the environment, the treated water is high in hardness and difficult to recycle, and the treatment cost of the waste residues is high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for treating arsenic in colored smelting waste acid by using jarosite slag and carbide slag, which utilizes low-cost jarosite slag and carbide slag to remove arsenic, can reduce the stockpiling amount of sludge in the waste acid treatment process, achieves the effect of treating waste by waste, and has the advantages of simple process operation, low production cost and wider market prospect.
A method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag comprises the following specific steps:
(1) mixing jarosite slag and carbide slag uniformly, drying and then carrying out ball milling until the granularity of the mixture is not higher than 0.56 μm to obtain mixed slag powder;
(2) adding the mixed slag powder obtained in the step (1) and potassium permanganate into contaminated acid, uniformly mixing, continuously introducing air under the stirring condition, and performing oxidation dearsenification reaction for 24-36 hours to obtain a solid-liquid mixture;
(3) and (3) performing solid-liquid separation on the solid-liquid mixture in the step (2) to obtain arsenic-containing solid and filtrate, stacking the arsenic-containing solid, and performing deep arsenic removal treatment on the filtrate.
The mass ratio of the jarosite slag to the carbide slag in the step (1) is (10:1) - (13: 4).
The solid-to-liquid ratio g: g: L of the mixed slag powder, the potassium permanganate and the waste acid in the step (2) is (8:0.8:1) - (11:1: 3).
And (3) stirring speed in the step (2) is 180-200 r/min.
The air flow in the step (2) is 0.5-1 m3/h。
The invention has the beneficial effects that:
(1) according to the invention, the arsenic removal is carried out by using the low-cost jarosite slag and the carbide slag, so that the stockpiling amount of sludge in the waste acid treatment process can be reduced, and the effect of treating wastes with wastes is achieved;
(2) the invention utilizes the low-cost jarosite slag and the carbide slag to remove arsenic, solves the problems of land occupation, management cost and the like of the stockpiling management treatment of the jarosite slag and the carbide slag in the prior art, and solves the problems of large waste residue amount, poor stability and easy toxicity leaching caused by treating waste acid by ferric lime salt;
(3) the invention adopts the jarosite slag and the carbide slag to treat the waste acid, has simple process operation and low production cost, and has wider market prospect.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: in the embodiment, the jarosite slag components are shown in table 1, the carbide slag components are shown in table 2, the waste acid is the waste acid containing a large amount of arsenic and other impurities generated after the smelting flue gas is washed in a sulfuric acid workshop of a certain zinc smelting plant in the southwest region, and the main components are shown in table 3;
TABLE 1 jarosite slag composition
TABLE 2 carbide slag composition
TABLE 3 dirty acid composition
A method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag comprises the following specific steps:
(1) mixing jarosite slag and carbide slag uniformly, drying and then carrying out ball milling until the granularity of the mixture is not higher than 0.56 μm to obtain mixed slag powder; wherein the mass ratio of jarosite slag to carbide slag is 10:1, the rotating speed of the ball mill is 760r/min, and the grinding time is 8 min;
(2) adding the mixed slag powder obtained in the step (1) and potassium permanganate into contaminated acid, uniformly mixing, continuously introducing air under the stirring condition, and performing oxidation dearsenification reaction for 24 hours to obtain a solid-liquid mixture; wherein the solid-to-liquid ratio g, g and L of the mixed slag powder, the potassium permanganate and the waste acid is 8:0.8:1, the stirring speed is 180r/min, and the air flow is 0.5m3/h；
(3) Solid-liquid separation is carried out on the solid-liquid mixture in the step (2) to obtain arsenic-containing solid and filtrate, the arsenic-containing solid is stockpiled and treated, and the filtrate is subjected to the next deep arsenic removal treatment;
toxicity Leaching tests of arsenic-containing solids were performed according to U.S. epa Method 1311-toxicity charateristic leach Procedure, provided by the united states environmental protection agency, with toxicity test results as shown in table 4,
TABLE 4 toxic leach results for arsenic-containing solids
The filtrate components are shown in Table 5;
TABLE 5 filtrate composition
In the filtrate of this example, the arsenic content was 124.1mg/L, and the removal rate of arsenic was 97.8%.
Example 2: in the embodiment, the jarosite slag components are shown in table 6, the carbide slag components are shown in table 7, the waste acid is the waste acid containing a large amount of arsenic and other impurities generated after the smelting flue gas is washed in a sulfuric acid workshop of a certain zinc smelting plant in the southwest region, and the main components are shown in table 8;
TABLE 6 jarosite slag composition
TABLE 7 carbide slag composition
TABLE 8 dirty acid composition
A method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag comprises the following specific steps:
(1) uniformly mixing jarosite slag and carbide slag, drying, and performing ball milling until the granularity of the mixture is not higher than 0.47 mu m to obtain mixed slag powder; wherein the mass ratio of jarosite slag to carbide slag is 13:4, the rotating speed of the ball mill is 910r/min, and the grinding time is 11 min;
(2) adding the mixed slag powder obtained in the step (1) and potassium permanganate into contaminated acid, uniformly mixing, continuously introducing air under the stirring condition, and performing oxidation dearsenification reaction for 36 hours to obtain a solid-liquid mixture; wherein the solid-to-liquid ratio g, g and L of the mixed slag powder, the potassium permanganate and the waste acid is 11:1:3, the stirring speed is 200r/min, and the air flow is 0.8m3/h；
(3) Solid-liquid separation is carried out on the solid-liquid mixture in the step (2) to obtain arsenic-containing solid and filtrate, the arsenic-containing solid is stockpiled and treated, and the filtrate is subjected to the next deep arsenic removal treatment;
toxicity Leaching tests of arsenic-containing solids were performed according to U.S. epa Method 1311-toxicity charateristic leach Procedure, provided by the united states environmental protection agency, with toxicity test results as shown in table 9,
TABLE 9 toxic leach results for arsenic-containing solids
The filtrate composition is shown in Table 10;
TABLE 10 filtrate composition
In the filtrate of this example, the arsenic content was 254.5mg/L, and the removal rate of arsenic was 97.5%.
Example 3: in the embodiment, the jarosite slag components are shown in table 11, the carbide slag components are shown in table 12, the waste acid is the waste acid containing a large amount of arsenic and other impurities generated after the smelting flue gas is washed in a sulfuric acid workshop of a certain zinc smelting plant in the southwest region, and the main components are shown in table 13;
TABLE 11 jarosite slag composition
TABLE 12 carbide slag composition
TABLE 13 dirty acid composition
A method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag comprises the following specific steps:
(1) mixing jarosite slag and carbide slag uniformly, drying and then carrying out ball milling until the granularity of the mixture is not higher than 0.42 μm to obtain mixed slag powder; wherein the mass ratio of the jarosite slag to the carbide slag is 11:2, the rotating speed of the ball mill is 835r/min, and the grinding time is 9.5 min;
(2) adding the mixed slag powder obtained in the step (1) and potassium permanganate into contaminated acid, uniformly mixing, continuously introducing air under the stirring condition, and performing oxidation dearsenification reaction for 30 hours to obtain a solid-liquid mixture; wherein the solid-to-liquid ratio g, g and L of the mixed slag powder, the potassium permanganate and the waste acid is 9: 0.9: 2, the stirring speed is 190r/min, and the air flow is 1m3/h；
(3) Solid-liquid separation is carried out on the solid-liquid mixture in the step (2) to obtain arsenic-containing solid and filtrate, the arsenic-containing solid is stockpiled and treated, and the filtrate is subjected to the next deep arsenic removal treatment;
toxicity Leaching tests of arsenic-containing solids were performed according to U.S. epa Method 1311-toxicity charateristic leach Procedure, provided by the united states environmental protection agency, with toxicity test results as shown in table 14,
TABLE 14 toxic leach results for arsenic-containing solids
The filtrate composition is shown in Table 15;
TABLE 15 filtrate composition
In the filtrate of this example, the arsenic content was 298.3mg/L, and the removal rate of arsenic was 97.7%.
Claims (2)
1. A method for treating arsenic in nonferrous smelting waste acid by using jarosite slag and carbide slag is characterized by comprising the following specific steps:
(1) mixing jarosite slag and carbide slag uniformly, drying and then carrying out ball milling until the granularity of the mixture is not higher than 0.56 μm to obtain mixed slag powder; wherein the mass ratio of the jarosite slag to the carbide slag is (10:1) - (13: 4);
(2) adding the mixed slag powder obtained in the step (1) and potassium permanganate into contaminated acid, uniformly mixing, continuously introducing air under the stirring condition, and performing oxidation dearsenization reaction for 24-36 hours to obtain a solid-liquid mixture; wherein the solid-to-liquid ratio g: g of the mixed slag powder, the potassium permanganate and the waste acid is (8:0.8:1) - (11:1:3), and the air flow is 0.5-1 m3/h；
(3) And (3) performing solid-liquid separation on the solid-liquid mixture in the step (2) to obtain arsenic-containing solid and filtrate, stacking the arsenic-containing solid, and performing deep arsenic removal treatment on the filtrate.
2. The method for treating arsenic in colored smelting waste acid by using jarosite slag and carbide slag according to claim 1, which is characterized by comprising the following steps: the stirring speed in the step (2) is 180-200 r/min.
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| CN111003775B (en) * | 2019-12-09 | 2022-05-27 | 昆明理工大学 | Method for treating arsenic in waste acid by copper slag and carbide slag |
| CN111925017B (en) * | 2020-08-17 | 2023-04-18 | 昆明理工大学 | Method for treating high-arsenic contaminated acid by using zinc slag |
| US11414334B2 (en) | 2020-10-09 | 2022-08-16 | United States Government, as represented by the Administrator of the U.S. EPA | Method for sequestering ions in an environmental matrix |
| US12097546B2 (en) | 2020-10-09 | 2024-09-24 | United States Government, as represented by the Administrator of the U.S. EPA | Method for sequestering ions in an environmental matrix |
| CN113620463A (en) * | 2021-08-12 | 2021-11-09 | 楚雄滇中有色金属有限责任公司 | Copper smelting waste acid gradient dearsenization treatment process |
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