JP2019131838A - METHOD FOR REMOVING SiO2 FROM SLURRY CONTAINING SILVER AND SiO2, AND PURIFICATION METHOD OF SILVER - Google Patents
METHOD FOR REMOVING SiO2 FROM SLURRY CONTAINING SILVER AND SiO2, AND PURIFICATION METHOD OF SILVER Download PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 66
- 239000004332 silver Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000002002 slurry Substances 0.000 title claims abstract description 45
- 238000000746 purification Methods 0.000 title claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title description 9
- 229910052681 coesite Inorganic materials 0.000 title 2
- 229910052906 cristobalite Inorganic materials 0.000 title 2
- 239000000377 silicon dioxide Substances 0.000 title 2
- 235000012239 silicon dioxide Nutrition 0.000 title 2
- 229910052682 stishovite Inorganic materials 0.000 title 2
- 229910052905 tridymite Inorganic materials 0.000 title 2
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 51
- 229910052802 copper Inorganic materials 0.000 claims description 44
- 239000010949 copper Substances 0.000 claims description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 43
- 238000005188 flotation Methods 0.000 claims description 42
- 238000002386 leaching Methods 0.000 claims description 24
- 241000628997 Flos Species 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000002516 radical scavenger Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 53
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000005909 Kieselgur Substances 0.000 description 5
- KDSXXMBJKHQCAA-UHFFFAOYSA-N disilver;selenium(2-) Chemical compound [Se-2].[Ag+].[Ag+] KDSXXMBJKHQCAA-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and in particular Chemical compound 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000010969 white metal Substances 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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Abstract
Description
本発明は、銀とＳｉＯ2を含むスラリーからＳｉＯ2を除去する方法に関するものであり、特に銅電解殿物又はその後の脱銅工程等を経た殿物、脱銅した殿物を対象に塩化浸出を行うことでＡｕ、Ｓｅ、Ｔｅなどの有価金属を浸出した塩化浸出残渣、又は塩化浸出残渣を鉄粉などの還元剤によって還元した残渣からＳｉＯ2を除去する方法に関するものである。 TECHNICAL FIELD The present invention relates to a method for removing SiO 2 from a slurry containing silver and SiO 2 , and in particular, chloride leaching for a copper electrolytic deposit, a deposit that has undergone a subsequent copper removal step, and a copper removal deposit. The present invention relates to a method for removing SiO 2 from a chlorinated leaching residue obtained by leaching valuable metals such as Au, Se and Te, or a residue obtained by reducing a chlorinated leaching residue with a reducing agent such as iron powder.
銅の電解精製においては、転炉からの粗銅を精製炉において９９．５％程度に精製し、鋳造した陽極（アノード）と陰極としてのステンレス板（パーマネントカソード）を電解槽に交互に数十枚一組で吊し、電解精製が実施される。パーマネントカソード上に電着した銅は電気銅と呼ばれ、周知の態様で事後処理されて商品化される。電解槽の底には陽極に含まれる不純物が泥状で沈積し、これは銅電解殿物（アノードスライム）と呼ばれている。 In electrolytic refining of copper, crude copper from the converter is refined to about 99.5% in the refining furnace, and cast anodes (anodes) and stainless steel plates (permanent cathodes) as cathodes are alternately placed in the electrolytic cell. Suspended as a set and electrolytic purification is performed. The copper electrodeposited on the permanent cathode is called electrolytic copper and is post-processed and commercialized in a well-known manner. Impurities contained in the anode are deposited in a muddy state at the bottom of the electrolytic cell, which is called a copper electrolytic deposit (anode slime).
銅電解殿物（アノードスライム）には金、銀などの貴金属元素が濃縮しており、銅電解殿物を湿式処理して貴金属元素を回収する方法が知られている。例えば、特許文献１（特開２００１−３１６７３５号公報）には、銅電解殿物に脱銅工程、塩化浸出工程及び金抽出工程を経由する予備処理を施し、さらに塩化浸出後、塩化銀主体の固体は水によるリパルプ後銀還元・精製工程に送り、鉄粉を添加して塩化銀から銀を還元する（還元工程）銅電解殿物の処理方法が記載されている。 A copper electrolytic deposit (anode slime) is enriched with noble metal elements such as gold and silver, and a method of recovering the noble metal element by wet-treating the copper electrolytic deposit is known. For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-316735), a copper electrolytic product is subjected to pretreatment via a copper removal step, a chloride leaching step, and a gold extraction step, and after leaching with chloride, A method for treating a copper electrolytic deposit is described in which a solid is sent to a silver reduction / purification process after repulping with water, and iron powder is added to reduce silver from silver chloride (reduction process).
また、銅電解によって生じる脱銅スライムに含まれるセレン化銀と硫酸鉛を効率よく分離し回収する方法として、特許文献２（特開２０１７−０６６４６４号公報）には、セレン化銀と硫酸鉛を含むスラリーに、パラフィンワックスを含む剥離剤を添加し、加熱下で撹拌した後に、捕集剤と起泡剤を添加して撹拌し、セレン化銀を含むフロスを形成し、一方、硫酸鉛はスラリーに残し、上記フロスを浮遊選鉱してセレン化銀を回収し、残留したスラリーに含まれる硫酸鉛と分離することを特徴とする銀と鉛の浮選分離方法が記載されている。 In addition, as a method for efficiently separating and recovering silver selenide and lead sulfate contained in the decopperized slime produced by copper electrolysis, Patent Document 2 (Japanese Patent Laid-Open No. 2017-066644) discloses silver selenide and lead sulfate. Add the release agent containing paraffin wax to the slurry containing and stir under heating, then add and stir the scavenger and foaming agent to form floss containing silver selenide, while lead sulfate is A method for flotation separation of silver and lead is described in which the floss is left behind in a slurry to collect silver selenide by flotation and separated from lead sulfate contained in the remaining slurry.
更に、近年リサイクル原料の処理量増加などの影響で、銅電解工程に入る不純物量が増加してきている。これにより銅電解に悪影響を及ぼす浮遊物質（ＳＳ）の発生量が増加するなどの影響があり、対応の一つとしてウルトラフィルタによって電解液をろ過し、浮遊物質（ＳＳ）の除去を行っている。ウルトラフィルタではろ過助剤として珪藻土を用いるが、この珪藻土が殿物に混入した場合、上記の還元銀中に珪藻土が混入することとなり、還元銀のＡｇ品位低下、そしてそれによる酸化炉の処理能力減少という悪影響を及ぼしている。そのため、銀化合物からの不純物除去方法の開発が望まれている。 Furthermore, in recent years, the amount of impurities entering the copper electrolysis process has increased due to the increase in the amount of recycled raw materials. This has the effect of increasing the amount of suspended matter (SS) that adversely affects copper electrolysis, and as one of the countermeasures, the electrolyte is filtered through an ultrafilter to remove suspended matter (SS). . Ultrafilter uses diatomaceous earth as a filter aid, but when this diatomaceous earth is mixed into the porcelain, diatomaceous earth is mixed in the above-mentioned reduced silver, the Ag quality of the reduced silver is lowered, and the treatment capacity of the oxidation furnace thereby It has an adverse effect of decrease. Therefore, development of a method for removing impurities from silver compounds is desired.
銅電解殿物又はその後の脱銅工程等を経た殿物には、珪藻土などのＳｉＯ2が含まれる。ＳｉＯ2は、粗銅に付着した離型剤に由来するものもあるほか、例えば銅電解工程で生じる電着異常の原因となる銅電解液中の浮遊物質（ＳＳ）を除去するために銅電解液をウルトラフィルタ装置へ供給して浮遊物質を除去することが行われる場合があるが、ウルトラフィルタ装置のろ過助剤である珪藻土が殿物に混入することも原因の一つである。 The copper electrolytic porcelain or the porcelain obtained through the subsequent copper removal step contains SiO 2 such as diatomaceous earth. In addition to those derived from a mold release agent attached to crude copper, SiO 2 is a copper electrolyte for removing suspended substances (SS) in the copper electrolyte that cause electrodeposition abnormalities that occur in the copper electrolysis process, for example. Is sometimes supplied to the ultrafilter device to remove suspended solids. One of the causes is that diatomaceous earth, which is a filter aid of the ultrafilter device, is mixed into the temple.
このような銀とＳｉＯ2を含む殿物についてそのまま処理する場合、ＳｉＯ2などの不純物によって必要処理量の増加、処理速度の低下といった問題が発生する。例えば、銅電解殿物に脱銅工程、塩化浸出工程及び還元工程を経由する処理を施して得られた殿物（還元銀）について、直接酸化炉で処理すると、銀品位が低いので酸化炉で処理しなければならない還元銀量が増加したり、処理した際に発生するスラグの量が多いために溶解時間が延びてタイムサイクルが長くなったりして、処理能力が減少してしまう。そのため、殿物からＳｉＯ2を除去するという要請がある。 When processing such a silver and SiO 2 deposit as it is, problems such as an increase in required processing amount and a reduction in processing speed occur due to impurities such as SiO 2 . For example, when a copper electrolytic product is processed through a copper removal step, a chloride leaching step, and a reduction step (reduced silver), if it is processed directly in an oxidation furnace, the silver quality is low. The amount of reduced silver that must be processed increases, or the amount of slag that is generated during processing increases, so that the melting time increases and the time cycle becomes longer, and the processing capacity decreases. Therefore, there is a request to remove SiO 2 from the temple.
また、特許文献２に記載される方法は、セレン化銀と硫酸鉛を効率よく分離し回収することができるとしても、ＳｉＯ2を除去することに着目しておらず、ＳｉＯ2を効果的に除去するには新しい方法が必要であった。 Further, the method described in Patent Document 2, even it is possible to silver selenide and lead sulfate efficiently separated and recovered, not focusing on the removal of SiO 2, the SiO 2 effectively A new method was needed to remove it.
そこで本発明は、銀とＳｉＯ2を含むスラリーからＳｉＯ2を効果的に除去する方法を提供することを課題とする。 Accordingly, an object of the present invention is to provide a method for effectively removing SiO 2 from a slurry containing silver and SiO 2 .
本発明者は、銀とＳｉＯ2を含むスラリーについて、特定の浮選工程を行うことで、ＳｉＯ2を効果的に除去できることを見出した。 The present inventors have, for the slurry containing silver and SiO 2, by performing a certain flotation step, it found to be able to effectively remove the SiO 2.
すなわち、本発明は以下のように特定される。
（１）銀とＳｉＯ2を含むスラリーからＳｉＯ2を除去する方法であって、
前記スラリーに捕集剤と起泡剤を添加して撹拌し、浮遊選鉱して銀を含むフロスを形成して銀を回収し、残留したスラリーに含まれるＳｉＯ2と分離する浮選工程
を含むことを特徴とする方法。
（２）前記捕集剤の添加量が１００ｇ／ｔ以上であることを特徴とする（１）に記載の方法。
（３）前記起泡剤の添加量が４０ｇ／ｔ以上であることを特徴とする（１）又は（２）に記載の方法。
（４）前記浮選工程におけるスラリーのｐＨは２〜４であることを特徴とする（１）〜（３）のいずれかに記載の方法。
（５）前記浮選工程により、前記スラリー中のＳｉＯ2を５０ｗｔ％以上除去することを特徴とする（１）〜（４）のいずれかに記載の方法。
（６）前記浮選工程の後、さらに回収された前記フロスに対して、０〜３００ｇ／ｔの捕集剤及び４０〜８０ｇ／ｔの起泡剤を添加して撹拌し、銀を浮遊選鉱することにより精選する工程を含むことを特徴とする（１）〜（５）のいずれかに記載の方法。
（７）銅電解殿物に脱銅工程及び塩化浸出工程を経由する処理を施し、得られた塩化浸出残渣を前記スラリーとし、前記浮選工程を行うことを特徴とする（１）〜（６）のいずれかに記載の方法。
（８）銅電解殿物に脱銅工程、塩化浸出工程及び還元工程を経由する処理を施し、得られた還元銀を前記スラリーとし、前記浮選工程を行うことを特徴とする（１）〜（６）のいずれかに記載の方法。
（９）（１）〜（８）のいずれかに記載の方法により銀とＳｉＯ2を含むスラリーからＳｉＯ2を除去した後、さらにＳｉＯ2を除去して得られたものを酸化炉により処理する工程を含む銀の精製方法。
That is, the present invention is specified as follows.
(1) A method of removing SiO 2 from a slurry containing silver and SiO 2 ,
A flotation step of adding a scavenger and a foaming agent to the slurry, stirring, flotation to form a floss containing silver, recovering silver, and separating it from SiO 2 contained in the remaining slurry; A method characterized by that.
(2) The method according to (1), wherein the addition amount of the scavenger is 100 g / t or more.
(3) The method according to (1) or (2), wherein the amount of the foaming agent added is 40 g / t or more.
(4) The method according to any one of (1) to (3), wherein the slurry has a pH of 2 to 4 in the flotation step.
(5) The method according to any one of (1) to (4), wherein 50 wt% or more of SiO 2 in the slurry is removed by the flotation step.
(6) After the flotation step, 0 to 300 g / t of a collecting agent and 40 to 80 g / t of a foaming agent are added to the recovered floss and stirred to stir silver. The method according to any one of (1) to (5), further comprising a step of selecting by performing.
(7) The copper electrolytic product is subjected to a treatment through a copper removal step and a chloride leaching step, and the resulting chlorination leaching residue is used as the slurry, and the flotation step is performed (1) to (6) ) Any one of the methods.
(8) The copper electrolytic deposit is subjected to a treatment through a copper removal step, a chlorination leaching step, and a reduction step, and the obtained reduced silver is used as the slurry, and the flotation step is performed. The method according to any one of (6).
(9) After removing SiO 2 from the slurry containing silver and SiO 2 by the method according to any one of (1) to (8), the product obtained by further removing SiO 2 is treated in an oxidation furnace. A method for purifying silver comprising a step.
本発明によれば、銀とＳｉＯ2を含むスラリーからＳｉＯ2を効果的に除去することができる。 According to the present invention, SiO 2 can be effectively removed from a slurry containing silver and SiO 2 .
銅電解殿物の処理フローの一例を図１に示す。図示するように、銅電解殿物に脱銅工程を経由する処理を施すことで脱銅後殿物が得られる。脱銅工程は、銅電解殿物の銅品位を低下させるための工程であり、具体的な手段は限定されないが、例えば、銅電解殿物中に含まれる銅を、銅電解工程の硫酸溶液を用いて常圧、空気吹き込み下、７０〜８５℃、１８〜２４時間浸出除去することにより実施することができる。 An example of the processing flow of the copper electrolytic deposit is shown in FIG. As shown in the drawing, the copper electrolytic deposit is subjected to a treatment via a copper removal step to obtain a post-copper removed deposit. The copper removal step is a step for lowering the copper quality of the copper electrolytic deposit, and the specific means is not limited. For example, the copper contained in the copper electrolytic deposit is replaced with the sulfuric acid solution of the copper electrolysis step. It can be carried out by leaching and removing at 70 to 85 ° C. for 18 to 24 hours under normal pressure and air blowing.
脱銅後殿物には、金、白金、銀、セレン、テルル、鉛などが含まれており、この不溶解物を塩酸と過酸化水素によって酸化溶解する（塩化浸出工程）。この塩化浸出工程によって、金、白金族は塩化物を形成して溶出するが、塩化銀は沈澱するので、固液分離して金、白金族と分離する。 After the copper removal, the deposit contains gold, platinum, silver, selenium, tellurium, lead and the like, and this insoluble matter is oxidized and dissolved with hydrochloric acid and hydrogen peroxide (chlorination leaching step). By this leaching step, the gold and platinum groups elute by forming chlorides, but since silver chloride precipitates, it is separated from the gold and platinum groups by solid-liquid separation.
塩化浸出工程により得られる塩化浸出残渣については、塩化銀などの銀を還元する還元工程を経由する処理を施し、還元銀が得られる。還元方法は特に限定されないが、例えば、塩化銀を鉄粉と反応させて銀を還元する方法を実施することができる。この還元銀をさらに酸化炉、銀電解により精製し、製品化することができる。 The leaching residue obtained by the leaching step is subjected to a treatment through a reduction step for reducing silver such as silver chloride to obtain reduced silver. Although the reduction method is not particularly limited, for example, a method of reducing silver by reacting silver chloride with iron powder can be carried out. This reduced silver can be further refined and commercialized by an oxidation furnace and silver electrolysis.
本発明において、塩化浸出残渣及び還元銀には、銀及びＳｉＯ2が含まれているので、これらをスラリーとして、前記スラリーに捕集剤と起泡剤を添加して撹拌し、浮遊選鉱して銀を含むフロスを形成して銀を回収し、残留したスラリーに含まれるＳｉＯ2と分離する浮選工程を経由する処理を施すことができる。また、塩化浸出工程を経た塩化浸出残渣、さらに還元工程を経た還元銀には、金や白金属元素の残存量が少なく、浮選を行ったテールに残る有価金属量が少なくなることが期待でき、またＣｕ、Ｓｅ、Ｔｅ等の不純物が除去され、浮選処理にかける原料の物量が減ることが期待できるから、塩化浸出残渣又は還元銀について本発明を実施することが好ましい。 In the present invention, since the chloride leaching residue and reduced silver contain silver and SiO 2 , these are used as a slurry, and a collecting agent and a foaming agent are added to the slurry, stirred, and subjected to flotation. A floss containing silver can be formed to recover the silver, and a treatment can be performed via a flotation process in which it is separated from SiO 2 contained in the remaining slurry. In addition, the leaching residue after the leaching process and the reduced silver after the leaching process have a small residual amount of gold and white metal elements, and it can be expected that the amount of valuable metal remaining in the flotation tail is reduced. In addition, since impurities such as Cu, Se, and Te can be removed and the amount of raw materials subjected to the flotation process can be expected to decrease, it is preferable to carry out the present invention with respect to chloride leaching residue or reduced silver.
銀とＳｉＯ2を含むスラリーに、捕集剤及び起泡剤を添加して撹拌する。捕集剤と起泡剤の種類は限定されないが、捕集剤としてＡｅｒｏｆｌｏａｔ＃２０８、起泡剤として４−メチル−２−ペンタノール（ＭＩＢＣ）が好ましい。捕集剤及び起泡剤を添加して撹拌し、浮遊選鉱して銀を含むフロスを形成して銀を回収する。一方、ＳｉＯ2は残留したスラリーに含まれるので、前述浮遊選鉱により銀と分離される。この浮選工程により、銀とＳｉＯ2を含むスラリーからＳｉＯ2が除去される。 A collecting agent and a foaming agent are added to a slurry containing silver and SiO 2 and stirred. Although the kind of a collection agent and a foaming agent is not limited, Aerofloat # 208 is preferable as a collection agent, and 4-methyl-2-pentanol (MIBC) is preferable as a foaming agent. The collector and the foaming agent are added and stirred, and the flotation containing silver is formed by flotation to collect silver. On the other hand, since SiO 2 is contained in the remaining slurry, it is separated from silver by the aforementioned flotation. By this flotation process, SiO 2 is removed from the slurry containing silver and SiO 2 .
浮選工程において、捕集剤の添加量が１００ｇ／ｔ以上であることが好ましい。これにより、銀の高い回収率を維持しつつ、ＳｉＯ2を除去することができる。この観点から、捕集剤の添加量は５００ｇ／ｔ以上であることが好ましく、１０００ｇ／ｔ以上であることがより好ましく、１５００ｇ／ｔ以上であることがさらにより好ましい。また、浮遊選鉱の効果を高めるには、前記起泡剤の添加量が４０ｇ／ｔ以上であることが好ましい。 In the flotation process, it is preferable that the amount of the collecting agent added is 100 g / t or more. Thereby, SiO 2 can be removed while maintaining a high silver recovery rate. In this respect, the amount of the collecting agent added is preferably 500 g / t or more, more preferably 1000 g / t or more, and even more preferably 1500 g / t or more. Moreover, in order to improve the effect of flotation, it is preferable that the addition amount of the said foaming agent is 40 g / t or more.
浮選工程において、浮選におけるスラリーのｐＨは２〜７の範囲内であることが好ましく、２〜４であることがより好ましい。スラリーのｐＨを４以下とすることにより、ＳｉＯ2の除去率をさらに高めることができる。 In the flotation step, the pH of the slurry in the flotation is preferably in the range of 2 to 7, and more preferably 2 to 4. By setting the pH of the slurry to 4 or less, the removal rate of SiO 2 can be further increased.
本発明によれば、浮選工程により、スラリー中のＳｉＯ2を５０ｗｔ％以上除去することができる。また、ＳｉＯ2の除去による必要処理量減少、溶解速度の向上などの効果を図る観点から、スラリー中のＳｉＯ2を５０ｗｔ％以上除去することがより好ましく、８０ｗｔ％以上除去することがさらにより好ましい。 According to the present invention, 50 wt% or more of SiO 2 in the slurry can be removed by the flotation process. Further, from the viewpoint of achieving the effect of reducing the required processing amount by removing SiO 2 and improving the dissolution rate, it is more preferable to remove 50 wt% or more of SiO 2 in the slurry, and even more preferable to remove 80 wt% or more. .
また、さらに浮選工程後のフロス中の銀品位を高めるため、０〜３００ｇ／ｔの捕集剤及び４０〜８０ｇ／ｔの起泡剤を添加して撹拌し、銀を浮遊選鉱することにより精選する工程を含むことができる。 Further, in order to further improve the silver quality in the floss after the flotation process, 0 to 300 g / t of a scavenger and 40 to 80 g / t of a foaming agent are added and agitated, and the silver is subjected to flotation. A step of selecting can be included.
さらに、銀とＳｉＯ2を含むスラリーからＳｉＯ2を除去した後、さらにＳｉＯ2を除去して得られたものを酸化炉により処理し、銀電解により精製し、製品化することができる。 Further, after removing SiO 2 from the slurry containing silver and SiO 2 , the product obtained by further removing SiO 2 can be treated in an oxidation furnace, purified by silver electrolysis, and commercialized.
＜実施例１＞
（１）スラリー液の作成
塩化浸出残渣及び還元銀のそれぞれに対し、４００ｇ量に水０．７Ｌを加え、常温でリパルプしてスラリー液にした。このスラリー液に、ｐＨ調整剤（硫酸又はＮａＯＨ溶液）を添加し規定のｐＨに調整した。
<Example 1>
(1) Preparation of slurry liquid To each of the chloride leaching residue and the reduced silver, 0.7 L of water was added to an amount of 400 g, and repulped at room temperature to obtain a slurry liquid. A pH adjuster (sulfuric acid or NaOH solution) was added to the slurry solution to adjust to a specified pH.
（２）浮選
スラリー液に対して規定量の気泡剤を添加して３分間のコンディショニング後、規定量の捕集剤を添加して１分間のコンディショニングを実施した。その後エアーの供給を行い、浮選を開始した。２分間の浮選中、発生したフロスはスキマーで自動掻き取りを行い、ろ過した。そのろ過滓をコンク（銀濃縮鉱）として回収した。なお、フロスの発生によってスラリー量が減少するが、都度水を補加して液面高さを一定に保った。残ったスラリーに捕集剤を追加で添加し、１分間のコンディショニングを実施後、浮選を継続した。また、コンクの状態を目視で確認し、起泡剤が少ないようであれば追い足しした。具体的には、捕集剤を累計７４９ｇ／ｔ添加した時点で起泡剤の追い足しを行った。目視でフロスの発生が確認できなくなるまで繰り返し実施した。実施例１を含む各実施例の一般的な浮選条件を表１に示し、実施例１の浮選条件は表２に示す。
(2) Flotation After adding a specified amount of foaming agent to the slurry and conditioning for 3 minutes, a specified amount of scavenger was added and conditioning was performed for 1 minute. After that, air was supplied and flotation started. During the flotation for 2 minutes, the generated floss was automatically scraped with a skimmer and filtered. The filter cake was recovered as conc (silver concentrated ore). In addition, although the amount of slurry decreased by generation | occurrence | production of floss, water was supplemented each time and the liquid level height was kept constant. An additional collecting agent was added to the remaining slurry, and after 1 minute of conditioning, flotation was continued. Moreover, the state of the conch was confirmed visually, and if there was little foaming agent, it added. Specifically, the foaming agent was added when the total amount of the collecting agent was 749 g / t. The test was repeated until the occurrence of floss could not be confirmed visually. Table 1 shows the general flotation conditions for each example including Example 1, and Table 2 shows the flotation conditions for Example 1.
上記実施例について、コンク及びテール内の銀及びＳｉＯ2の品位を、銀は乾式分析（灰吹き法）により、ＳｉＯ2はアルカリ融解−ＩＣＰ発光分光分析法（ＩＣＰ−ＡＥＳ、セイコーインスツル株式会社製、ＳＰＳ７７００）により測定した。分析結果から分配率を計算し、その結果を表３に示す。 For the above example, silver and quality of the SiO 2 in concentrated and the tail, the silver dry analytical (Haifukihou), SiO 2 is alkali fusion -ICP emission spectroscopy (ICP-AES, Seiko Instruments Inc. Manufactured by SPS7700). The distribution ratio is calculated from the analysis result, and the result is shown in Table 3.
＜実施例２＞
さらに、上記実施例１と同様の方法で、表４に示す条件で還元銀について粗選と精選を行い得られるコンク及びテール内の銀及びＳｉＯ2の品位と分配率を前述の方法により測定し、その結果を表５に示す。なお、粗選とは実施例１と同様の手法で浮選を実施することであり、精選とは粗選で得られたフロスをさらに浮選することで銀の品位を更に高める方法である。
<Example 2>
Further, the quality and distribution rate of silver and SiO 2 in the conch and tail obtained by performing rough selection and fine selection on the reduced silver under the conditions shown in Table 4 in the same manner as in Example 1 above were measured by the method described above. The results are shown in Table 5. In addition, rough selection is to perform flotation by the same method as in Example 1, and fine selection is a method to further improve the quality of silver by further flotating the floss obtained by rough selection.
＜実施例３＞
さらに、上記実施例１と同様の方法で、開始ｐＨを変えて浮選を行い得られるコンク及びテール内の銀及びＳｉＯ2の品位と分配率を前述の方法により測定し、その結果を表６に示す。ｐＨが４．１以上になるとＳｉＯ2がコンクに分配されやすくなり、ＳｉＯ2の除去を目的とした本法ではｐＨが低い方が有利であることが明らかである。
<Example 3>
Further, the quality and distribution rate of silver and SiO 2 in the conch and tail obtained by flotation by changing the starting pH in the same manner as in Example 1 above were measured by the above-mentioned methods, and the results are shown in Table 6. Shown in pH is likely that SiO 2 becomes 4.1 or more is distributed in conc, it is clear that it is advantageous pH is low with this method for the purpose of removing the SiO 2.
上記各実施例によれば、浮選工程の導入により、銀品位を向上させることができ、銀の高い回収率を維持したまま、ＳｉＯ2を効果的に除去することができ、その後の酸化炉等に供される必要処理量を削減することができたことが分かった。 According to each of the above embodiments, by introducing the flotation process, the silver quality can be improved, and SiO 2 can be effectively removed while maintaining a high silver recovery rate, and the subsequent oxidation furnace It was found that the required amount of processing provided for etc. could be reduced.
Claims (9)
前記スラリーに捕集剤と起泡剤を添加して撹拌し、浮遊選鉱して銀を含むフロスを形成して銀を回収し、残留したスラリーに含まれるＳｉＯ2と分離する浮選工程
を含むことを特徴とする方法。 A method for removing SiO 2 from a slurry containing silver and SiO 2 , comprising:
A flotation step of adding a scavenger and a foaming agent to the slurry, stirring, flotation to form a floss containing silver, recovering silver, and separating it from SiO 2 contained in the remaining slurry; A method characterized by that.
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| JP2010518102A (en) * | 2007-02-07 | 2010-05-27 | サイテク・テクノロジー・コーポレーシヨン | New dithiocarbamate scavengers and their use in ore body beneficiation. |
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| JPS61174341A (en) * | 1985-01-29 | 1986-08-06 | Mitsubishi Metal Corp | Method for refining slime produced by electrolysis of copper |
| JPH0418946A (en) * | 1990-05-11 | 1992-01-23 | Dow Chem Co:The | Recovery of valuable mineral by floating ore in bubbling solution for separation |
| JP2010518102A (en) * | 2007-02-07 | 2010-05-27 | サイテク・テクノロジー・コーポレーシヨン | New dithiocarbamate scavengers and their use in ore body beneficiation. |
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