CN108330285A - A kind of lead anode slurry chloridizing leach solution defluorination method - Google Patents
A kind of lead anode slurry chloridizing leach solution defluorination method Download PDFInfo
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- CN108330285A CN108330285A CN201810091762.5A CN201810091762A CN108330285A CN 108330285 A CN108330285 A CN 108330285A CN 201810091762 A CN201810091762 A CN 201810091762A CN 108330285 A CN108330285 A CN 108330285A
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- leachate
- anode slurry
- lead anode
- leach solution
- chloridizing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Removal Of Specific Substances (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of lead anode slurry chloridizing leach solution defluorination methods, include the following steps：（1）Measure the fluorine-containing leachate through chloridizing with controlled voltage leaching process；（2）To step（1）Described in BaCl is added in leachate2Solution, and be stirred to react 1 ~ 9 hour with the speed of 100 ~ 150 r/min at 20 ~ 50 DEG C, obtain the leachate containing white precipitate；（3）After the completion of being stirred to react, filtration step（2）Described in the leachate containing white precipitate, obtain filtrate, gained filtrate is the leachate obtained through lead anode slurry chloridizing leach solution defluorination method.Using the method for the present invention, the fluorine in leachate can be simply and efficiently removed, fluoride removing rate can reach as high as 98% in 3 hours.
Description
Technical field
The present invention relates to the wet-treating field of lead anode slurry more particularly to a kind of lead anode slurry chloridizing leach solution fluorine removal sides
Method.
Background technology
Lead anode slurry is the by-product of electrolytic lead refining process, typically contain higher lead, silver, arsenic, antimony and part zinc,
The elements such as bismuth, copper, selenium, tellurium, gold.To the processing of lead anode slurry mainly to obtain the noble metals such as gold and silver, other are each for synthetical recovery
Kind valuable metal.The processing method of lead anode slurry mainly has pyrogenic attack, wet-treating and wet method-three kinds of pyrogenic process Combined Treatment,
Three kinds of techniques are respectively suitable for the lead anode slurry of heterogeneity.For high antimony-lead anode mud, mostly uses soaked in chloride system greatly
Go out to realize expensive, base metal separation.Such as a kind of a kind of high antimony-lead anode mud wet-treating disclosed on Chinese patent
Method, Publication No. CN101787440A, by high antimony lead sun of the produced antimony content in lead electrolytic process between 40%-75%
Pole mud is placed in hydrochloric acid medium, is leached using two sections of adverse current chloridizing with controlled voltage, the oxidation-reduction potential control of one section of potassium cloride terminal
System is in 200 ~ 300 mV, and the oxidation reduction potential control of two sections of potassium cloride terminals is in 400 ~ 450 mV, 99.5% gold and 99%
Silver be enriched in two sections of potassium cloride slags, can further be recycled.
By the way that SbCl is added5, sodium chlorate is as oxidant, or use " hydrochloric acid medium controlling potential potassium cloride-leaching
Liquid reduction-arsenic removal distillation " technological process can effectively realize expensive, base metal separation in high antimony-lead anode mud.However, due to
Lead electrolytic solution ingredient is fluosilicic acid-lead fluorosilicate solution, therefore carries a large amount of fluosilicic acid in the earth of positive pole formed.In chlorination
After leaching, fluosilicic acid and fluosilicate enter leachate.The presence of fluosilicic acid and fluosilicate is unfavorable for soaking in chloridizing leach solution
The extraction for going out valuable metal in liquid can cause distillation pipeline to block during follow-up arsenic removal distillation due to fluosilicic acid decomposition, right
Wastewater treatment also brings along negative effect.Therefore, it is necessary to carry out fluorine removal operation to lead anode slurry chloridizing leach solution in advance
's.
Invention content
The present invention is to overcome the presence of fluosilicic acid and fluosilicate in above-mentioned chloridizing leach solution to be unfavorable in leachate
The extraction of valuable metal and distillation pipeline can be caused to block during follow-up arsenic removal distillation, wastewater treatment be also brought along negative
The problem that face is rung, provides a kind of lead anode slurry chloridizing leach solution defluorination method, can effectively realize lead anode slurry chloridizing leach solution
The purpose of fluorine removal.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of lead anode slurry chloridizing leach solution defluorination method, includes the following steps：
（1）Measure the fluorine-containing leachate through chloridizing with controlled voltage leaching process；The leachate is made of the ion of following concentration：Sb from
Sub 450 ~ 500 g/L, As ion 18 ~ 26 g/L, SiF6 2-20 ~ 25g/L of ion, 1 ~ 9 g/L, Cu ion of Pb ions, 5 ~ 15 g/L,
15 ~ 30 g/L, Ag ion of Bi ions 0.1 ~ 1.5 g/L, H+4-6 mol/L and Cl：4-6 mol/L；
（2）To step（1）Described in BaCl is added in leachate2Solution, and it is stirred to react 1 with the speed of 100 ~ 150 r/min ~
9 hours, obtain the leachate containing white precipitate；
（3）After the completion of being stirred to react, filtration step（2）Described in the leachate containing white precipitate, obtain filtrate, gained filtrate
The leachate as obtained through lead anode slurry chloridizing leach solution defluorination method.The solvent of leachate is water.
Preferably, step（1）Described in leachate, fluoride ion includes SiF6 2-。
Preferably, step（2）In, described be stirred to react carries out under 20 ~ 50 DEG C of constant temperature.
Preferably, step（2）In, BaCl2After solution is added to leachate, BaCl2It is a concentration of in leachate
SiF6 2-1.5 ~ 2.5 times of concentration.Excessive BaCl is added2, and BaCl is made by stirring2With fluosilicic acid root and other fluosilicic acid
Reactant salt.
Preferably, step（2）In, BaCl2After solution is added to leachate, BaCl2It is a concentration of in leachate
SiF6 2-2.0 ~ 2.2 times of concentration.
Preferably, step（2）In, the mixing speed is 120 r/min.
Preferably, step（2）In, mixing time is 3 ~ 5 hours.
Preferably, step（3）In, with Buchner funnel or the filter device filtering of similar functions can be realized containing white
The leachate of precipitation.
Since barium fluosilicate has minimum solubility in all fluosilicates（About 0.26 g/L）, can be by soaking
Go out and BaCl is added in liquid2Realize the removal of fluosilicic acid, at the same time, the fluosilicate of other types is also due to Ba2+Deposit
And be converted into more stable barium fluosilicate precipitation, to realize the purpose of lead anode slurry chloridizing leach solution fluorine removal.For warp
Lead anode slurry leachate after chloridizing with controlled voltage leaches can be carried out using technical scheme of the present invention at simple, efficient fluorine removal
Reason, fluoride removing rate can reach 90 % or more.Under the conditions of the fluorine removal after preferably, fluoride removing rate can reach as high as in 3 hours
98%, the fluorine in leachate is substantially removed.
Description of the drawings
Fig. 1 is lead anode slurry chloridizing leach solution defluorination method flow chart of the present invention.
Specific implementation mode
Technical solution of the present invention is described in further detail below by specific embodiment, agents useful for same in embodiment
It is purchased in market or is obtained by routine experiment method.
Embodiment 1：
A kind of lead anode slurry chloridizing leach solution defluorination method, includes the following steps：（1）Measure 200 mL through chloridizing with controlled voltage leaching at
The leachate of reason, the leachate constituent component and each component it is a concentration of consisting of：481.75 g/L, As ion of Sb ions
22.36 g/L、SiF6 2-：22.56 g/L, Pb ion, 4.27 g/L, Cu ion, 9.10 g/L, Bi ion 24.72 g/L, Ag from
Son 0.71, H+5 mol/L and Cl-5 mol/L；
（2）To step（1）Described in BaCl is added in leachate2Solution, and with the speed of 120 r/min, 20 °C of constant temperature item
It is stirred reaction 3 hours under part, obtains the leachate containing white precipitate, wherein by BaCl2Solution is added to leachate
Afterwards, BaCl2A concentration of SiF in leachate6 2-2.0 times of concentration；
（3）After the completion of being stirred to react, with filtered on buchner funnel step（2）Described in the leachate containing white precipitate, filtered
Liquid, gained filtrate are the leachate obtained through lead anode slurry chloridizing leach solution defluorination method.
The content of fluorine in filtrate is detected using fluoride ion selective electrode, fluorine content is down to by 22.56 g/L after testing
0.42 g/L（It is calculated by the volume before fluorine removal）, fluoride removing rate is up to 98.1%.
Embodiment 2
A kind of lead anode slurry chloridizing leach solution defluorination method, includes the following steps：（1）Measure 200 mL through chloridizing with controlled voltage leaching at
The leachate of reason, the leachate constituent component and each component it is a concentration of consisting of：450 g/L, As ion of Sb ions, 18 g/
L、SiF6 2-23.32 g/L, Pb ion, 1 g/L, Cu ion, 5 g/L, Bi ion, 15 g/L, Ag ion 0.1 g/L, H+ 4 mol/
L and Cl-4 mol/L；
（2）To step（1）Described in BaCl is added in leachate2Solution, and with the speed of 100 r/min, 50 °C of constant temperature item
It is stirred reaction 9 hours under part, obtains the leachate containing white precipitate, wherein by BaCl2Solution is added to leachate
Afterwards, BaCl2A concentration of SiF in leachate6 2-1.5 times of concentration；
（3）After the completion of being stirred to react, with funnel filtration step（2）Described in the leachate containing white precipitate, obtain filtrate, institute
It is the leachate obtained through lead anode slurry chloridizing leach solution defluorination method to obtain filtrate.
The content of fluorine in filtrate is detected using fluoride ion selective electrode, fluorine content is down to by 23.32g/L after testing
0.96g/L（It is calculated by the volume before fluorine removal）, fluoride removing rate is up to 95.8%.
Embodiment 3
A kind of lead anode slurry chloridizing leach solution defluorination method, includes the following steps：（1）Measure 200mL through chloridizing with controlled voltage leaching at
The leachate of reason, the leachate constituent component and each component it is a concentration of consisting of：Sb ions500 g/L, As ions 26
g/L、SiF6 2-9 g/L, Cu ion of 21.46g/L, Pb ion, 15 g/L, Bi ion, 30 g/L, Ag ion 0.1 ~ 1.5, H+
6 mol/L and Cl-6 mol/L；
（2）To step（1）Described in BaCl is added in leachate2Solution, and with the speed of 150 r/min, 30 °C of constant temperature item
It is stirred reaction 4 hours under part, obtains the leachate containing white precipitate, wherein by BaCl2Solution is added to leachate
Afterwards, BaCl2A concentration of SiF in leachate6 2-2.5 times of concentration；
（3）After the completion of being stirred to react, with funnel filtration step（2）Described in the leachate containing white precipitate, obtain filtrate, institute
It is the leachate obtained through lead anode slurry chloridizing leach solution defluorination method to obtain filtrate.
The content of fluorine in filtrate is detected using fluoride ion selective electrode, fluorine content is down to by 21.46 g/L after testing
0.93 g/L（It is calculated by the volume before fluorine removal）, fluoride removing rate is up to 95.7%.
Embodiment 4
A kind of lead anode slurry chloridizing leach solution defluorination method, includes the following steps：（1）Measure 200mL through chloridizing with controlled voltage leaching at
The leachate of reason, the leachate constituent component and each component it is a concentration of consisting of：476.75 g/L, As ion of Sb ions
22.36 g/L、SiF6 2-24.50 g/L, Pb ion, 3.65 g/L, Cu ion, 9.10 g/L, Bi ion 24.72 g/L, Ag from
0.71 g/L, H of son+6 mol/L and Cl-6 mol/L；
（2）To step（1）Described in BaCl is added in leachate2Solution, and with the speed of 130 r/min, 40 °C of constant temperature item
It is stirred reaction 1 hour under part, obtains the leachate containing white precipitate, wherein by BaCl2Solution is added to leachate
Afterwards, BaCl2A concentration of SiF in leachate6 2-2.2 times of concentration；
（3）After the completion of being stirred to react, with funnel filtration step（2）Described in the leachate containing white precipitate, obtain filtrate, institute
It is the leachate obtained through lead anode slurry chloridizing leach solution defluorination method to obtain filtrate.
The content of fluorine in filtrate is detected using fluoride ion selective electrode, fluorine content is down to 0.66 by 24.50g/L after testing
g/L（It is calculated by the volume before fluorine removal）, fluoride removing rate is up to 97.3%.
Claims (8)
1. a kind of lead anode slurry chloridizing leach solution defluorination method, which is characterized in that include the following steps：
（1）Measure the fluorine-containing leachate through chloridizing with controlled voltage leaching process；
（2）To step（1）Described in BaCl is added in leachate2Solution, and it is stirred to react 1 ~ 9 with the speed of 100 ~ 150 r/min
Hour, obtain the leachate containing white precipitate；
（3）After the completion of being stirred to react, filtration step（2）Described in the leachate containing white precipitate, obtain filtrate, gained filtrate
The leachate as obtained through lead anode slurry chloridizing leach solution defluorination method.
2. a kind of lead anode slurry chloridizing leach solution defluorination method according to claim 1, which is characterized in that step（1）In
In the leachate, fluoride ion includes SiF6 2-。
3. a kind of lead anode slurry chloridizing leach solution defluorination method according to claim 1 or 2, which is characterized in that step（2）
In, described be stirred to react carries out under 20 ~ 50 °C of constant temperature.
4. a kind of lead anode slurry chloridizing leach solution defluorination method according to claim 2, which is characterized in that step（2）In,
BaCl2After solution is added to leachate, BaCl2A concentration of SiF in leachate6 2-1.5 ~ 2.5 times of concentration.
5. a kind of lead anode slurry chloridizing leach solution defluorination method according to claim 4, which is characterized in that step（2）In,
BaCl2After solution is added to leachate, BaCl2A concentration of SiF in leachate6 2-2.0 ~ 2.2 times of concentration.
6. a kind of lead anode slurry chloridizing leach solution defluorination method according to any one of claim 1,2,4 or 5, special
Sign is, step（2）In, the mixing speed is 120 r/min.
7. a kind of lead anode slurry chloridizing leach solution defluorination method according to claim 6, which is characterized in that step（2）In,
Mixing time is 3 ~ 5 hours.
8. a kind of lead anode slurry chloridizing leach solution defluorination method according to claim 7, which is characterized in that step（3）In,
Contain the leachate of white precipitate with filtered on buchner funnel.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373474A (en) * | 2011-10-31 | 2012-03-14 | 合肥晶澳太阳能科技有限公司 | Method for recycling wool making/etching solution |
| CN102515170A (en) * | 2011-12-16 | 2012-06-27 | 天津市泰亨气体有限公司 | Method for preparing tetrafluorosilane by fluorosilicic acid process |
| CN105154681A (en) * | 2015-08-21 | 2015-12-16 | 西北矿冶研究院 | Process for recovering fluorine and zinc from steelmaking soot |
| CN106185855A (en) * | 2016-06-30 | 2016-12-07 | 云南磷化集团有限公司 | A kind of feed grade phosphoric acid by wet process deep-purifying method |
| CN106830244A (en) * | 2017-02-27 | 2017-06-13 | 中南大学 | A kind of method that fluorine and acid are separated and recovered from acidic fluoride-containing waste water |
-
2018
- 2018-01-30 CN CN201810091762.5A patent/CN108330285A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373474A (en) * | 2011-10-31 | 2012-03-14 | 合肥晶澳太阳能科技有限公司 | Method for recycling wool making/etching solution |
| CN102515170A (en) * | 2011-12-16 | 2012-06-27 | 天津市泰亨气体有限公司 | Method for preparing tetrafluorosilane by fluorosilicic acid process |
| CN105154681A (en) * | 2015-08-21 | 2015-12-16 | 西北矿冶研究院 | Process for recovering fluorine and zinc from steelmaking soot |
| CN106185855A (en) * | 2016-06-30 | 2016-12-07 | 云南磷化集团有限公司 | A kind of feed grade phosphoric acid by wet process deep-purifying method |
| CN106830244A (en) * | 2017-02-27 | 2017-06-13 | 中南大学 | A kind of method that fluorine and acid are separated and recovered from acidic fluoride-containing waste water |
Non-Patent Citations (2)
| Title |
|---|
| 钟扬等: "铅阳极泥氯化浸出液除氟研究", 《有色金属（冶炼部分）》 * |
| 阳杨等: "湿法磷酸浓缩后的氟分配及脱氟工艺研究", 《磷肥与复肥》 * |
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