CN102586622A - Method for producing electrolytic zinc by comprehensively recycling high-chlorine high-fluorine lead and antimony smelting waste residue - Google Patents
Method for producing electrolytic zinc by comprehensively recycling high-chlorine high-fluorine lead and antimony smelting waste residue Download PDFInfo
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- CN102586622A CN102586622A CN201210073883XA CN201210073883A CN102586622A CN 102586622 A CN102586622 A CN 102586622A CN 201210073883X A CN201210073883X A CN 201210073883XA CN 201210073883 A CN201210073883 A CN 201210073883A CN 102586622 A CN102586622 A CN 102586622A
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- Prior art keywords
- chlorine
- fluorine
- zinc
- waste residue
- lead
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 22
- 239000011701 zinc Substances 0.000 title claims abstract description 22
- 239000002699 waste material Substances 0.000 title claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 title abstract description 18
- 239000000460 chlorine Substances 0.000 title abstract description 18
- 229910052787 antimony Inorganic materials 0.000 title abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000003723 Smelting Methods 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000004064 recycling Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229940037003 alum Drugs 0.000 claims abstract description 5
- 238000002386 leaching Methods 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005272 metallurgy Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- QXXKGIVXMAGBDV-UHFFFAOYSA-N [Pb].[Cl].[F] Chemical compound [Pb].[Cl].[F] QXXKGIVXMAGBDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000006298 dechlorination reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract 4
- 238000005406 washing Methods 0.000 abstract 2
- 239000003518 caustics Substances 0.000 abstract 1
- 238000000280 densification Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000010802 sludge Substances 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DLXJYRBLNXRRBT-UHFFFAOYSA-N [Cl].[F].[Zn] Chemical compound [Cl].[F].[Zn] DLXJYRBLNXRRBT-UHFFFAOYSA-N 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 chlorine fluorine lead-zinc Chemical compound 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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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- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a method for producing electrolytic zinc by comprehensively recycling high-chlorine high-fluorine lead and antimony smelting waste residue. The method is characterized by comprising the following steps of: preparing zinc hypoxide powder from the high-chlorine high-fluorine lead and antimony smelting waste residue by using a rotary kiln, slurrying the zinc hypoxide powder, removing fluorine and chlorine through two-stage alkaline washing, neutrally leaching obtained caustic sludge by using sulfuric acid, performing alum settlement treatment to obtain a purified liquid, and treating by the conventional electrodeposition process to obtain the electrolytic zinc. The invention provides the preparation of the zinc hypoxide powder from lead and antimony waste residue by using the rotary kiln, and the removal of the fluorine and the chlorine through a densification kiln or two-stage alkaline washing after the zinc hypoxide powder is slurried for the first time; the invention is characterized in that: the method is high in production capacity, the fluorine and the chlorine are completely removed, the treated purified liquid can remove a large number of harmful elements and meet electrodeposition requirements, the qualified electrolytic zinc is produced, the recovery rate of zinc reaches 84 percent, various kinds of valuable elements can be recovered, and the like; and the method can be used for the smelting and recovery industry of the lead and antimony waste residue.
Description
Technical field
The present invention relates to a kind of smelting process, more particularly, the present invention relates to the method that a kind of high chlorine fluorine lead and tin metallurgy waste residue comprehensive reutilization is produced electrolytic zinc.
Background technology
The lead and tin metallurgy waste residue is general waste resource in China at present, and it contains multiple valuable metals such as zinc, lead, indium, has higher recovery value.Present treatment process generally adopts waves the Wurz concentration method.The secondary zinc oxide of this method institute output, its composition are very complicated, can not be used for the electric zinc production of traditional process separately, and very very little proportioning is used.The lead and tin metallurgy waste residue is waved the secondary zinc oxide that the enrichment of Wurz concentration method is come out, and its impurity is higher, and detrimental impurity such as silicon, lead, arsenic, antimony, iron, (divalence) fluorine, chlorine are higher than tens times even the hundreds of times that the upper limit requires in the traditional technology, can not be used for batching especially in a large number.And iron (divalence), silicon are high, are difficult to solid-liquid separation, and fluorine, chlorine be high, corrode pole plate easily, pole plate is increased consumes the difficulty of delaminating.At present, plumbous antimony waste residue does not also have better zinc enriching method, makes it to adapt to the electrolytic zinc production technique.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, the plumbous antimony waste residue of a kind of high chlorine fluorine zinc enriching method is provided, make it to adapt to the production of electrolytic zinc.
The object of the invention is achieved through following technical proposals.
High chlorine fluorine lead-zinc smelting waste residue is through rotary kiln output secondary zinc oxide powder; After the pulp of secondary zinc oxide powder through density kiln or two sections alkali cleaning dechlorination fluorine; The alkaline residue of gained is handled through heavy alum and promptly being purified liquid through the neutral leaching of sulfuric acid, can the output zinc ingot metal through conventional electrodeposition process.
The invention has the beneficial effects as follows:
1, the fluorine and the chlorine that all contain excess in melting waste slag and the coal; With the secondary zinc oxide powder that melting waste slag is produced through rotary kiln, the content summation of fluorine and chlorine often reaches 0.5%-1% usually, and so high fluorine and chlorine do not have effective solution in conventional process of enriching; Roasting method commonly used; Removal effect and not obvious makes more than the fluorine cl content Chang Gaoda 2000mg/L in the scavenging solution, exceeds ten times than 200mg/L processing requirement.Fluorine, corrosion yin, yang pole plate when the chlorine height causes electrowinning zinc increase pole plate consumption, and the very difficulty of delaminating.The present invention adopts density kiln or two sections alkali cleaning defluorinate chlorine; Fluorine, chlorine and soda ash attack in the secondary zinc oxide powder are removed, come compared with roasting method, fluorine chlorine removes thoroughly clean more; Through the experiment proof; Behind density kiln or the two sections alkali cleaning defluorinate chlorine, the fluorine cl content has satisfied the requirement of electrodeposition process less than 200mg/L in the scavenging solution.
2, the present invention leaches and heavy alum through sulfuric acid is neutral behind secondary zinc oxide powder density kiln or two sections alkali cleaning defluorinates, chlorine again, effectively removes wherein lead, arsenic, indium, silver, antimony, iron etc. to the deleterious impurity element of electrodeposition, and can comprehensively reclaim.The scavenging solution of gained satisfies the requirement of zinc electrodeposition process, has avoided the too high problem that causes electric zinc burning plate of detrimental impurity elements such as arsenic, lead.And the problem of the too high solid-liquid separation difficulty that causes of iron silicon.
3, the present invention produces the secondary zinc oxide powder through rotary kiln first, and treatment capacity is big, can satisfy the needs of scale prodn.
4, zinc recovery 84% of the present invention, valuable elements such as recyclable indium, iron, lead simultaneously.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The present invention is done the explanation in a step below in conjunction with accompanying drawing.
Embodiment 1: with granularity is that lead and tin metallurgy waste residue and the coal of 1-5mm places in the rotary kiln, 1200 ℃ of temperature, carries out volatilization roasting under the condition of 1.5 hours time, and volatile matter gets into bagroom and gathers dust, the secondary zinc oxide powder.The secondary zinc oxide powder is that 5: 1 ratio water carries out pulp in solid-to-liquid ratio; With soda ash PH is transferred to 8 then; At temperature 70-80 ℃, carry out two sections alkali cleaning defluorinate chlorine under the condition of 1 hour time, leach through hot acid by routine then; The heavy alum of jarosite is handled and is purified liquid, promptly obtains electrolytic zinc through electrodeposition again.
Embodiment 2: inferior chlorine is inserted the density kiln through zinc powder, 900 ℃ of temperature, carries out the density kiln under 2～4 hours time condition, the dechlorination fluorine, and all the other are with embodiment 1.
Claims (1)
1. high chlorine fluorine lead and tin metallurgy waste residue comprehensive reutilization is produced electrolytic zinc; It is characterized in that; High chlorine fluorine lead and tin metallurgy waste residue is through rotary kiln output secondary zinc oxide powder, and through density kiln or two sections alkali cleaning dechlorination fluorine, the alkaline residue of gained is through the neutral leaching of sulfuric acid after the pulp of secondary zinc oxide powder; Handle through heavy alum again and promptly be purified liquid, can the output zinc ingot metal through conventional electrodeposition process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210073883XA CN102586622A (en) | 2012-03-20 | 2012-03-20 | Method for producing electrolytic zinc by comprehensively recycling high-chlorine high-fluorine lead and antimony smelting waste residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210073883XA CN102586622A (en) | 2012-03-20 | 2012-03-20 | Method for producing electrolytic zinc by comprehensively recycling high-chlorine high-fluorine lead and antimony smelting waste residue |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102586622A true CN102586622A (en) | 2012-07-18 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210073883XA Pending CN102586622A (en) | 2012-03-20 | 2012-03-20 | Method for producing electrolytic zinc by comprehensively recycling high-chlorine high-fluorine lead and antimony smelting waste residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102586622A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014350A (en) * | 2012-12-22 | 2013-04-03 | 泸溪蓝天冶化有限责任公司 | Recycling method of zinc hypoxide |
| CN108103315A (en) * | 2017-12-05 | 2018-06-01 | 广西生富锑业科技股份有限公司 | A kind of method that zinc is recycled in the caustic fusion slag from jamesonite |
| 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 |
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| CN1272553A (en) * | 1999-05-04 | 2000-11-08 | 沈奕林 | New process for recovering metals of indium, iron, silver and tin from high-indium high-iron zinc preparation concentrate |
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| CN101157987A (en) * | 2007-11-01 | 2008-04-09 | 中南大学 | A method for processing complex sub-zinc oxide raw materials to produce electric zinc |
| CN101413059A (en) * | 2008-11-27 | 2009-04-22 | 郴州丰越有色金属冶炼有限公司 | Process for comprehensively and efficiently recycling zinc and indium in indium raffinate |
| 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 |
| CN101608266A (en) * | 2009-07-23 | 2009-12-23 | 广西冶金研究院 | A kind of cleaning collecting method and device thereof of the zinc oxide that volatilizees |
| CN102094126A (en) * | 2010-11-10 | 2011-06-15 | 白银有色集团股份有限公司 | Process for smelting zinc with wet method of high temperature and high acid-jarosite iron removing-iron vitriol slag pickling by two stages |
| CN102828051A (en) * | 2012-09-07 | 2012-12-19 | 白银有色集团股份有限公司 | Desiliconization process in zinc hydrometallurgy |
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2012
- 2012-03-20 CN CN201210073883XA patent/CN102586622A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272553A (en) * | 1999-05-04 | 2000-11-08 | 沈奕林 | New process for recovering metals of indium, iron, silver and tin from high-indium high-iron zinc preparation concentrate |
| CN1587060A (en) * | 2004-09-22 | 2005-03-02 | 冯碧朗 | Method for producing zinc suboxide |
| CN1804062A (en) * | 2006-01-11 | 2006-07-19 | 黄有余 | Crude indium and active zinc oxide co-production process |
| CN101078053A (en) * | 2007-06-23 | 2007-11-28 | 王树楷 | Method for extracting metal indium, zinc and bismuth from blast furnace gas ash |
| CN101157987A (en) * | 2007-11-01 | 2008-04-09 | 中南大学 | A method for processing complex sub-zinc oxide raw materials to produce electric zinc |
| 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 |
| CN101413059A (en) * | 2008-11-27 | 2009-04-22 | 郴州丰越有色金属冶炼有限公司 | Process for comprehensively and efficiently recycling zinc and indium in indium raffinate |
| CN101608266A (en) * | 2009-07-23 | 2009-12-23 | 广西冶金研究院 | A kind of cleaning collecting method and device thereof of the zinc oxide that volatilizees |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014350A (en) * | 2012-12-22 | 2013-04-03 | 泸溪蓝天冶化有限责任公司 | Recycling method of zinc hypoxide |
| CN103014350B (en) * | 2012-12-22 | 2014-12-10 | 泸溪蓝天冶化有限责任公司 | Recycling method of zinc hypoxide |
| CN108103315A (en) * | 2017-12-05 | 2018-06-01 | 广西生富锑业科技股份有限公司 | A kind of method that zinc is recycled in the caustic fusion slag from jamesonite |
| 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 |
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Application publication date: 20120718 |