CN102851510A - Method for removing chlorine and fluorine from smelting smoke ash containing chlorine and fluorine - Google Patents
Method for removing chlorine and fluorine from smelting smoke ash containing chlorine and fluorine Download PDFInfo
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- CN102851510A CN102851510A CN2012103111914A CN201210311191A CN102851510A CN 102851510 A CN102851510 A CN 102851510A CN 2012103111914 A CN2012103111914 A CN 2012103111914A CN 201210311191 A CN201210311191 A CN 201210311191A CN 102851510 A CN102851510 A CN 102851510A
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- fluorine
- chlorine
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- back extraction
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Abstract
The invention discloses a method for removing chlorine and fluorine from smelting smoke ash containing chlorine and fluorine. The method is characterized in that the method uses the smelting smoke as a raw material, and is realized through the technological processes of leaching with sulfuric acid, extraction with a tertiary amine N235, back extraction with ammonia water, and fluorine removal with quicklime. After the leaching is carried out through sulfuric acid, a clear leachate is obtained after liquid-solid separation; the extracting separation operation of fluorine and chlorine in the leachate is completed through selecting an alkyl tertiary amine N235 as an extractor and sulfonated kerosene as solvent oil to obtain an N235 organic phase containing fluorine and chlorine, and a chlorine extraction liquor; a regenerated N235 organic phase and a strip liquor are obtained through the back extraction of the N235 organic phase by the ammonia water; and a calcium fluoride residue and a filtrate containing ammonium chloride are obtained through adding quicklime and carrying out press filtrating separation. The method which can effectively remove soluble fluorine and chlorine from the smoke ash has the advantages of low operation cost and no wastewater discharge; fluorine and chlorine in the smoke ash are obtained in a calcium fluoride and ammonium chloride manner, the calcium fluoride residue can be used as a fluorine extraction raw material, and the ammonium chloride can be used as a fertilizer; and the N235 strip liquor can be used as a wet smelting zinc raw material liquid.
Description
Technical field
The invention belongs to technical field of smelting, relate to a kind of method of the fluorine that from the containing chlorine fluorine smelting ash, dechlorinates.
Background technology
Smelting ash is the solid waste that produces in the copper pyrometallurgy process, wherein is rich in heavy metal zinc, copper, cadmium, lead, tin, also contains a large amount of chlorine, fluorine, silicon, aluminium, arsenic, calcium halophosphate activated by antimony andmanganese, nickel etc.Imurity-removal chlorine fluorine is the technical bottleneck in the hydrometallurgy cigarette ash technique.
Prior art CN102108445A relates to a kind of fluorine chlorine removal methods of zinc oxide fume dust.It is to adopt Na
2CO
3With NaOH zinc oxide fume dust is carried out alkali cleaning, with zinc oxide fume dust and solid Na
2CO
3Mix, add the solution that the entry high-speed stirring is dissolved into slag, make ZnCl in the flue dust
2, ZnF
2, PbCl
2In metal form the carbonate solid slag, chlorine, fluorine then are dissolved in the solution with the form of sodium salt, adopt the method need to consume a large amount of alkali and sodium carbonate salt, wastewater discharge is large.
CN101307385 is for the chloride flue dust of generation in melting zinc, lead, the tin process, and the method for its employing water washing removes the chlorine in the raw material.Adopt the method waste water generation of washing large, and the valuable metal ions of solubility loses in the flue dust with discharge of wastewater, soluble heavy metal ions and salt are with the discharge of wastewater contaminate environment.
CN102220480A is a kind of method of utilizing the microwave calcining zinc oxide fumes to take off fluorine and chlorine removal, carries out roasting under the microwave condition by zinc oxide fumes is placed, after temperature reaches 550～650 ℃, and insulation 10～30min; In the roasting process material is stirred; And microwave cavity bled, keep normal pressure.Microwave calcining mode energy consumption is large, and industrialization is difficulty relatively.
CN101649396 provides a kind of method of utilizing secondary zinc oxide cigarette ash efficiently to remove F, Cl, secondary zinc oxide cigarette ash adds the dilution heat of sulfuric acid Acidified granulation, after the rotary kiln baking reinforcement removes F, Cl, the roasting powder is neutral the leaching first, terminal point pH control 3.0～3.5, end point determination leach liquor As, Sb, F content, leach liquor adds FeSO
47H
2Then O adds the hydrogen peroxide oxidation neutralization except As, Sb, adds at last milk of lime and detects without Fe to terminal
2+, As, Sb, F.Adopt rotary kiln dechlorination energy consumption high, the maintenance of equipment amount is large, invests highly, and operating environment is poor.
Summary of the invention
The object of the invention is to utilize sulfuric acid leaching-extracting-back extraction Technology, realized under low operating cost, separating impurity fluorine chlorine in the smelting ash, solved the technical bottleneck in the smelting ash wet method Zn extraction process.Thereby provide a kind of method of the fluorine that from the containing chlorine fluorine smelting ash, dechlorinates.
To achieve these goals, technical scheme of the present invention is to be raw material with smelting ash, realizes by following four technique processes: (1) sulfuric acid leaching; (2) tertiary amine N 235 extractions; (3) ammoniacal liquor back extraction; (4) unslaked lime defluorinate.Behind the sulfuric acid leaching, through liquid-solid separation, the leach liquor that obtains clarifying; Select alkyl tertiary amine N235 to make extraction agent, sulfonated kerosene is solvent oil, finishes the extracting and separating operation to fluorine chlorine in the leach liquor, obtains N235 organic phase and the remaining liquid of extraction chlorine of fluorine-containing chlorine; With ammoniacal liquor the N235 organic phase is carried out back extraction, N235 organic phase and anti-raffinate obtain regenerating; Add unslaked lime, press filtration separates, and gets Calcium Fluoride (Fluorspan) slag and containing ammonium chloride filtrate.
1. sulfuric acid leaching;
According to the liquid-solid mass ratio 5 ~ 10:1 of sulfuric acid liquid leaching agent and smelting ash, leaching agent Free Acid 30 ~ 70 g/L, under 20 ~ 100 ℃ of temperature, reaction 1 ~ 4 h, Leaching reaction endpoint pH 1.5 ~ 3.5, through liquid-solid separation, the leach liquor that obtains clarifying;
2. tertiary amine N 235 extractions;
Select alkyl tertiary amine N235 to make extraction agent, sulfonated kerosene is solvent oil, configuration 10 ~ 30% volume proportion organic phases, the 1. extracting and separating of fluorine chlorine operation in the leach liquor of completing steps in box mixing-settler, 20 ~ 50 ℃ of its service temperatures, extraction phase is than O/A=1 ~ 4:1, and extraction time 5 ~ 10 min obtain N235 organic phase and the remaining liquid of extraction chlorine of fluorine-containing chlorine;
3. ammoniacal liquor back extraction;
With mass concentration 10 ~ 20% ammoniacal liquor to step 2. gained N235 organic phase carry out back extraction, O/A=10 ~ 30:1 is compared in back extraction, 20 ~ 50 ℃ of service temperatures, back extraction times 5 ~ 10 min, N235 organic phase and anti-raffinate obtain regenerating;
4. unslaked lime defluorinate;
Add the 3. unslaked lime of 5 ~ 10 times of fluorine quality in the anti-raffinate of gained of step, press filtration separates, and gets Calcium Fluoride (Fluorspan) slag and containing ammonium chloride filtrate.Gained Calcium Fluoride (Fluorspan) slag can be used as carries the fluorine raw material, and the filtrate containing ammonium chloride can be used as Fertilizer application.
Beneficial effect of the present invention
(1) adopts leaching-extracting-back extraction technique, can effectively remove the fluorine chlorine of solubility in the ash drop;
(2) take this process economics running cost low, non-wastewater discharge, environmental friendliness;
(3) fluorine, chlorine are with Calcium Fluoride (Fluorspan), ammonium chloride open circuit in the cigarette ash, and gained Calcium Fluoride (Fluorspan) slag can be used as carries the fluorine raw material, and ammonium chloride can be used as fertilizer;
(4) the remaining liquid of N235 extraction can be used as the zinc hydrometallurgy stock liquid.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention 1.
Embodiment
The present invention is by the following examples can the invention will be further described, yet scope of the present invention is not limited to following embodiment.
Embodiment 1: operate according to technique shown in 1 figure.
A kind of typical smelting ash chemical composition sees Table 1.
1. leach
According to the liquid-solid mass ratio 10:1 of sulfuric acid liquid leaching agent and smelting ash, leaching agent Free Acid 40 g/L under 70 ℃ of temperature, react 4 h, Leaching reaction terminal point pH value 3.5, and through liquid-solid separation, the leach liquor that obtains clarifying;
2. tertiary amine N 235 extractions
Select alkyl tertiary amine N235 to make extraction agent, sulfonated kerosene is solvent oil, configuration 10 ~ 30% volume proportion organic phases, the 1. extracting and separating of fluorine chlorine operation in the leach liquor of completing steps in box mixing-settler, 20 ℃ of its service temperatures, extraction phase is than O/A=2:1, and extraction time 5 min obtain N235 organic phase and the remaining liquid of extraction chlorine of fluorine-containing chlorine;
3. ammoniacal liquor back extraction
With mass concentration 20% ammoniacal liquor to step 2. gained N235 organic phase carry out back extraction, O/A=15:1 is compared in back extraction, 20 ℃ of service temperatures, back extraction times 10 min, N235 organic phase and anti-raffinate obtain regenerating;
4. unslaked lime defluorinate
Add the 3. unslaked lime of 10 times of fluorine quality in the anti-raffinate of gained of step, press filtration separates, and gained Calcium Fluoride (Fluorspan) slag can be used as carries the fluorine raw material, and the filtrate containing ammonium chloride can be used as Fertilizer application.
Claims (6)
1. the method for a dechlorination fluorine from the containing chlorine fluorine smelting ash is characterized in that: be raw material with the containing chlorine fluorine smelting ash, by following four technique processes realization: (1) sulfuric acid leaching; (2) tertiary amine N 235 extractions; (3) ammoniacal liquor back extraction; (4) unslaked lime defluorinate.
According to claim 1 a kind of from the containing chlorine fluorine smelting ash dechlorination fluorine method, the technique that it is characterized in that sulfuric acid leaching is: according to the liquid-solid mass ratio 5 ~ 10:1 of sulfuric acid liquid leaching agent and smelting ash, leaching agent Free Acid 30 ~ 70 g/L, under 20 ~ 100 ℃ of temperature, reaction 1 ~ 4 h, Leaching reaction endpoint pH 1.5 ~ 3.5, through liquid-solid separation, the leach liquor that obtains clarifying.
According to claim 1 a kind of from the containing chlorine fluorine smelting ash dechlorination fluorine method, the technique that it is characterized in that tertiary amine N 235 extractions is: select alkyl tertiary amine N235 to make extraction agent, sulfonated kerosene is solvent oil, configuration 10 ~ 30% volume proportion organic phases, in box mixing-settler, finish the extracting and separating operation to fluorine chlorine in the leach liquor behind the sulfuric acid leaching, 20 ~ 50 ℃ of its service temperatures, extraction phase is than O/A=1 ~ 4:1, and extraction time 5 ~ 10 min obtain N235 organic phase and the remaining liquid of extraction chlorine of fluorine-containing chlorine.
According to claim 1 a kind of from the containing chlorine fluorine smelting ash dechlorination fluorine method, the technique that it is characterized in that the ammoniacal liquor back extraction is: with mass concentration 10 ~ 20% ammoniacal liquor the technique gained N235 organic phase of tertiary amine N 235 extractions is carried out back extraction, O/A=10 ~ 30:1 is compared in back extraction, 20 ~ 50 ℃ of service temperatures, back extraction times 5 ~ 10 min, N235 organic phase and anti-raffinate obtain regenerating.
According to claim 1 a kind of from the containing chlorine fluorine smelting ash dechlorination fluorine method, the technique that it is characterized in that the unslaked lime defluorinate is: the unslaked lime that adds 5 ~ 10 times of fluorine quality in the anti-raffinate of technique gained of ammoniacal liquor back extraction, press filtration separates, and gets Calcium Fluoride (Fluorspan) slag and containing ammonium chloride filtrate.
According to claim 1 a kind of from the containing chlorine fluorine smelting ash method of dechlorination fluorine, it is characterized in that realizing by following technique process:
1. sulfuric acid leaching;
According to the liquid-solid mass ratio 5 ~ 10:1 of sulfuric acid liquid leaching agent and smelting ash, leaching agent Free Acid 30 ~ 70 g/L, under 20 ~ 100 ℃ of temperature, reaction 1 ~ 4 h, Leaching reaction endpoint pH 1.5 ~ 3.5, through liquid-solid separation, the leach liquor that obtains clarifying;
2. tertiary amine N 235 extractions;
Select alkyl tertiary amine N235 to make extraction agent, sulfonated kerosene is solvent oil, configuration 10 ~ 30% volume proportion organic phases, the 1. extracting and separating of fluorine chlorine operation in the leach liquor of completing steps in box mixing-settler, 20 ~ 50 ℃ of its service temperatures, extraction phase is than O/A=1 ~ 4:1, and extraction time 5 ~ 10 min obtain N235 organic phase and the remaining liquid of extraction chlorine of fluorine-containing chlorine;
3. ammoniacal liquor back extraction;
With mass concentration 10 ~ 20% ammoniacal liquor to step 2. gained N235 organic phase carry out back extraction, O/A=10 ~ 30:1 is compared in back extraction, 20 ~ 50 ℃ of service temperatures, back extraction times 5 ~ 10 min, N235 organic phase and anti-raffinate obtain regenerating;
4. unslaked lime defluorinate;
Add the 3. unslaked lime of 5 ~ 10 times of fluorine quality in the anti-raffinate of gained of step, press filtration separates, and gets Calcium Fluoride (Fluorspan) slag and containing ammonium chloride filtrate, and gained Calcium Fluoride (Fluorspan) slag can be used as carries the fluorine raw material, and the filtrate containing ammonium chloride can be used as Fertilizer application.
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| CN2012103111914A CN102851510A (en) | 2012-08-29 | 2012-08-29 | Method for removing chlorine and fluorine from smelting smoke ash containing chlorine and fluorine |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060561A (en) * | 2013-01-15 | 2013-04-24 | 云南祥云飞龙有色金属股份有限公司 | Method for removing chlorine from chlorine-containing zinc sulfate solution |
| CN103451449A (en) * | 2013-08-30 | 2013-12-18 | 红河锌联科技发展有限公司 | Activation extraction separation method for fluorine and chloride ions in zinc sulfate solution |
| CN107447110A (en) * | 2017-07-07 | 2017-12-08 | 北京盖雅环境科技有限公司 | A kind of preparation method of LITHIUM BATTERY manganese sulfate |
| CN108642282A (en) * | 2018-03-26 | 2018-10-12 | 杨秋良 | The recovery method of vanadium in a kind of fluorine-containing extracting vanadium from stone coal pickle liquor |
| CN113122734A (en) * | 2021-03-12 | 2021-07-16 | 广西壮族自治区固体废物和化学品环境管理中心 | Smelting method for removing fluorine and chlorine from secondary zinc oxide |
| CN118637589A (en) * | 2024-08-14 | 2024-09-13 | 中国科学院过程工程研究所 | Method for in-situ extraction, separation and recovery of fluorine in acidolysis process of phosphorite |
| CN118637589B (en) * | 2024-08-14 | 2024-10-29 | 中国科学院过程工程研究所 | Method for in-situ extraction, separation and recovery of fluorine in acidolysis process of phosphorite |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007054828A (en) * | 2005-07-25 | 2007-03-08 | Mitsubishi Materials Corp | Treating method of fly ash |
| CN101078053A (en) * | 2007-06-23 | 2007-11-28 | 王树楷 | Method for extracting metal indium, zinc and bismuth from blast furnace gas ash |
| JP2009179841A (en) * | 2008-01-30 | 2009-08-13 | Mitsubishi Materials Corp | Method for treating molten fly ash |
| CN101580901A (en) * | 2008-05-15 | 2009-11-18 | 甘肃众星锌业有限公司 | Method for refining zinc by using slag containing zinc |
| CN102220480A (en) * | 2011-05-20 | 2011-10-19 | 昆明理工大学 | Method for removing fluorine and chlorine from zinc oxide smoke dust by microwave roasting |
-
2012
- 2012-08-29 CN CN2012103111914A patent/CN102851510A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007054828A (en) * | 2005-07-25 | 2007-03-08 | Mitsubishi Materials Corp | Treating method of fly ash |
| CN101078053A (en) * | 2007-06-23 | 2007-11-28 | 王树楷 | Method for extracting metal indium, zinc and bismuth from blast furnace gas ash |
| JP2009179841A (en) * | 2008-01-30 | 2009-08-13 | Mitsubishi Materials Corp | Method for treating molten fly ash |
| CN101580901A (en) * | 2008-05-15 | 2009-11-18 | 甘肃众星锌业有限公司 | Method for refining zinc by using slag containing zinc |
| CN102220480A (en) * | 2011-05-20 | 2011-10-19 | 昆明理工大学 | Method for removing fluorine and chlorine from zinc oxide smoke dust by microwave roasting |
Non-Patent Citations (1)
| Title |
|---|
| 窦传龙: "溶剂萃取法从硫酸锌溶液中萃取脱氯的试验研究", 《湖南有色金属》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060561A (en) * | 2013-01-15 | 2013-04-24 | 云南祥云飞龙有色金属股份有限公司 | Method for removing chlorine from chlorine-containing zinc sulfate solution |
| CN103060561B (en) * | 2013-01-15 | 2014-10-22 | 云南祥云飞龙有色金属股份有限公司 | Method for removing chlorine from chlorine-containing zinc sulfate solution |
| CN103451449A (en) * | 2013-08-30 | 2013-12-18 | 红河锌联科技发展有限公司 | Activation extraction separation method for fluorine and chloride ions in zinc sulfate solution |
| CN103451449B (en) * | 2013-08-30 | 2014-07-02 | 红河锌联科技发展有限公司 | Activation extraction separation method for fluorine and chloride ions in zinc sulfate solution |
| CN107447110A (en) * | 2017-07-07 | 2017-12-08 | 北京盖雅环境科技有限公司 | A kind of preparation method of LITHIUM BATTERY manganese sulfate |
| CN108642282A (en) * | 2018-03-26 | 2018-10-12 | 杨秋良 | The recovery method of vanadium in a kind of fluorine-containing extracting vanadium from stone coal pickle liquor |
| CN113122734A (en) * | 2021-03-12 | 2021-07-16 | 广西壮族自治区固体废物和化学品环境管理中心 | Smelting method for removing fluorine and chlorine from secondary zinc oxide |
| CN113122734B (en) * | 2021-03-12 | 2022-10-21 | 广西壮族自治区固体废物和化学品环境管理中心 | Smelting method for removing fluorine and chlorine from secondary zinc oxide |
| CN118637589A (en) * | 2024-08-14 | 2024-09-13 | 中国科学院过程工程研究所 | Method for in-situ extraction, separation and recovery of fluorine in acidolysis process of phosphorite |
| CN118637589B (en) * | 2024-08-14 | 2024-10-29 | 中国科学院过程工程研究所 | Method for in-situ extraction, separation and recovery of fluorine in acidolysis process of phosphorite |
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Application publication date: 20130102 |