JP5016410B2 - Copper solution purification method and copper production method - Google Patents
Copper solution purification method and copper production method Download PDFInfo
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- JP5016410B2 JP5016410B2 JP2007203502A JP2007203502A JP5016410B2 JP 5016410 B2 JP5016410 B2 JP 5016410B2 JP 2007203502 A JP2007203502 A JP 2007203502A JP 2007203502 A JP2007203502 A JP 2007203502A JP 5016410 B2 JP5016410 B2 JP 5016410B2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 313
- 239000010949 copper Substances 0.000 title claims description 237
- 229910052802 copper Inorganic materials 0.000 title claims description 234
- 238000000034 method Methods 0.000 title claims description 76
- 238000000746 purification Methods 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000000243 solution Substances 0.000 claims description 67
- 238000004090 dissolution Methods 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 238000005868 electrolysis reaction Methods 0.000 claims description 35
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 15
- 229910052785 arsenic Inorganic materials 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 12
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- 238000002386 leaching Methods 0.000 description 17
- 229910000510 noble metal Inorganic materials 0.000 description 16
- 238000000227 grinding Methods 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000010970 precious metal Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 238000005507 spraying Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000670 limiting effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000009692 water atomization Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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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- Electrolytic Production Of Metals (AREA)
Description
本発明は、銅溶解液中から銅電解の阻害元素である砒素等の不純物を十分に取り除くことができる銅溶解液の浄液方法及び銅溶解液の浄液方法を用いた銅の製造方法に関する。 The present invention relates to a copper solution purification method that can sufficiently remove impurities such as arsenic that is an element inhibiting copper electrolysis from a copper solution, and a copper production method using the copper solution purification method. .
従来より、粗銅を精製銅（電気銅）にする電解精製プロセスとしては、例えば、図１に示すように、電解槽４内の銅電解液３中で、粗銅からなるアノード１から高純度の銅板からなるカソード２に直流電流を流すことにより、アノード１中の銅分が溶解してカソード２に移行し、カソード板の表面に精製銅（純銅）として析出するものである。
前記粗銅中には、通常貴金属が含まれており、これら貴金属は電解精製過程でスライムとして電解槽の底に沈降し堆積している。この沈降し堆積したスライムを別途処理することにより貴金属、及び不純物を回収している。
Conventionally, as an electrolytic purification process for converting crude copper into purified copper (electrocopper), for example, as shown in FIG. 1, in a copper electrolyte solution 3 in an electrolytic cell 4, a high purity copper plate is obtained from an anode 1 made of crude copper. When a direct current is passed through the cathode 2 made of the material, the copper content in the anode 1 is dissolved and transferred to the cathode 2 and deposited as purified copper (pure copper) on the surface of the cathode plate.
The crude copper usually contains noble metals, and these noble metals settle and deposit on the bottom of the electrolytic cell as slime during the electrolytic purification process. Precious metals and impurities are recovered by separately treating the sedimented and accumulated slime.
しかし、前記従来の方法では、アノードとカソードとの間隔は、単位面積当たりの生産性を向上させるためには、短いことが好ましいが、短すぎるとショートが発生しやすくなる。そして、ショートが発生すると電流効率が低下すると共に、ノジュール（こぶ）等の発生により、カソードの外観形状の悪化、スライムの巻き込み等により不純物の増加が生じる。
また、電解による銅析出量は電流の大きさに比例するので、電流密度を大きくすると生産能力が増加するが、スライム及び銅電解液の巻き込みにより電気銅中の不純物レベルが増加し、電気銅の品質が悪化する。また、アノード隣接部分の銅電解液でＣｕイオンが飽和し、導電性のないＣｕＳＯ４・５Ｈ２Ｏの結晶が析出す、Ｃｕの溶出ができなくなる不働態現象が発生し、電解効率上の制約が生じる。更に、粗銅中に微量に含まれている貴金属は最終工程までいかないと回収することができず、貴金属の回収が遅くなってしまうという課題がある。
However, in the conventional method, the distance between the anode and the cathode is preferably short in order to improve the productivity per unit area. However, if the distance is too short, a short circuit is likely to occur. When a short circuit occurs, current efficiency is reduced, and generation of nodules or the like causes an increase in impurities due to deterioration of the external shape of the cathode, entrainment of slime, and the like.
In addition, since the amount of copper deposited by electrolysis is proportional to the magnitude of the current, increasing the current density increases the production capacity, but the inclusion of slime and copper electrolyte increases the level of impurities in the electrolytic copper, and Quality deteriorates. In addition, Cu ions are saturated in the copper electrolyte solution adjacent to the anode, non-conductive CuSO 4 · 5H 2 O crystals are precipitated, and a passive state phenomenon in which Cu cannot be eluted occurs. Occurs. Furthermore, there is a problem in that the noble metal contained in a trace amount in the crude copper cannot be recovered unless the final process is reached, and the recovery of the noble metal is delayed.
更に、銅品位の高い高純度銅を直接製造できる方法として、例えば特許文献１に記載の方法が開示されている。この方法は、銅アノードを用いた銅の電解精製後に得られる銅濃度が２５ｇ／Ｌ以上の硫酸酸性の銅電解液から、金属基体に貴金属系金属酸化物が被覆されたものからなる不溶性アノードを用いて、電解採取により、電気銅を得る。好ましくは、不溶性アノードは、酸化イリジウムを被覆したチタン板である。また、好ましくは、アノード及びカソードに対して平行に銅電解液を流すものである。
しかし、この方法においては、鋳造したアノード板を用いているので、大型の溶解設備が必要となり、不純物を電解前に除去することは困難であるのが実情である。
Furthermore, as a method capable of directly producing high-purity copper having high copper quality, for example, a method described in Patent Document 1 is disclosed. In this method, an insoluble anode composed of a sulfuric acid acidic copper electrolyte having a copper concentration of 25 g / L or more obtained after electrolytic purification of copper using a copper anode is coated with a noble metal based metal oxide. Used to obtain electrolytic copper by electrowinning. Preferably, the insoluble anode is a titanium plate coated with iridium oxide. Preferably, the copper electrolyte is made to flow in parallel with the anode and the cathode.
However, in this method, since a cast anode plate is used, a large melting equipment is required, and it is actually difficult to remove impurities before electrolysis.
本発明は、従来における諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、銅溶解液中から銅電解の阻害元素である砒素等の不純物の含有量を低減でき、粗銅粉を用いた銅の製造方法に使用する銅電解液を効率よく製造することができる銅溶解液の浄液方法及び銅の製造方法を提供することを目的とする。 An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention can reduce the content of impurities such as arsenic that is an element inhibiting copper electrolysis from a copper solution, and efficiently produce a copper electrolyte used in a method for producing copper using crude copper powder. An object of the present invention is to provide a copper solution purification method and a copper production method.
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ 粗銅粉を溶解してなる銅溶解液から、一次残渣を濾別した濾液に粗銅粉を添加し、遊離硫酸濃度を下げ、前記濾液中の不純物を除去して銅電解液を調製することを特徴とする銅溶解液の浄液方法である。
＜２＞ 不純物が、Ａｓ、Ｓｂ及びＳｎから選択される少なくとも１種である前記＜１＞に記載の銅溶解液の浄液方法である。
＜３＞ 銅電解液の銅濃度が、７０ｇ／Ｌ〜１００ｇ／Ｌである前記＜１＞から＜２＞のいずれかに記載の銅溶解液の浄液方法である。
＜４＞ 銅電解液の遊離硫酸濃度が、５ｇ／Ｌ以下である前記＜１＞から＜３＞のいずれかに記載の銅溶解液の浄液方法である。
＜５＞ 少なくとも、粉体化工程と、銅粉溶解工程と、濾過工程と、浄液工程と、電解工程とを含む銅の製造方法であって、
前記浄液工程が、前記＜１＞から＜４＞のいずれかに記載の銅溶解液の浄液方法により行われることを特徴とする銅の製造方法である。
Means for solving the problems are as follows. That is,
<1> From the copper solution obtained by dissolving the crude copper powder, the crude copper powder is added to the filtrate obtained by filtering the primary residue, the free sulfuric acid concentration is lowered, and impurities in the filtrate are removed to prepare a copper electrolyte. This is a method for purifying a copper solution.
<2> The method for purifying a copper solution according to <1>, wherein the impurity is at least one selected from As, Sb, and Sn.
<3> The copper solution purification method according to any one of <1> to <2>, wherein the copper concentration of the copper electrolyte is 70 g / L to 100 g / L.
<4> The method for purifying a copper solution according to any one of <1> to <3>, wherein the free sulfuric acid concentration of the copper electrolyte is 5 g / L or less.
<5> A copper production method including at least a pulverization step, a copper powder dissolution step, a filtration step, a liquid purification step, and an electrolysis step,
The method for producing copper, wherein the liquid purification step is performed by the copper solution purification method according to any one of <1> to <4>.
本発明によると、従来における問題を解決することができ、銅溶解液中から銅電解の阻害元素である砒素等の不純物の含有量を低減でき、粗銅粉を用いた銅の製造方法に使用する銅電解液を効率よく製造することができる銅溶解液の浄液方法及び該銅溶解液の浄液方法を用いた銅の製造方法を提供することができる。 According to the present invention, conventional problems can be solved, and the content of impurities such as arsenic, which is an element inhibiting copper electrolysis, can be reduced from the copper solution, which is used in a method for producing copper using crude copper powder. A copper solution purification method capable of efficiently producing a copper electrolyte and a copper production method using the copper solution purification method can be provided.
（銅溶解液の浄液方法）
本発明の銅溶解液の浄液方法は、粗銅粉を溶解してなる銅溶解液から、一次残渣を濾別した濾液に粗銅粉を添加し、遊離硫酸濃度を下げ、前記濾液中の不純物を除去して銅電解液を調製するものである。
ここで、前記銅溶解液とは、銅の電解精製に用いる銅電解液に調整前の銅を溶解した液であり、不純物の除去、遊離硫酸濃度を下げ、銅濃度を電解用に調整などが済んでいないものを意味し、本発明においては、銅の電解精製に用いる銅電解液とは区別している。
(Copper solution purification method)
In the copper solution purification method of the present invention, from the copper solution obtained by dissolving the crude copper powder, the crude copper powder is added to the filtrate obtained by filtering the primary residue, the free sulfuric acid concentration is lowered, and the impurities in the filtrate are reduced. It removes and prepares a copper electrolyte solution.
Here, the copper solution is a solution in which copper before adjustment is dissolved in a copper electrolyte used for electrolytic purification of copper, such as removal of impurities, reduction of free sulfuric acid concentration, adjustment of copper concentration for electrolysis, etc. In the present invention, it is distinguished from the copper electrolyte used for the electrolytic purification of copper.
＜粗銅粉＞
前記銅溶解液の製造方法に用いる粗銅粉としては、特に制限はなく、目的に応じて適宜選択することができるが、以下のようにして粉体化処理されたものが好ましい。
<Coarse copper powder>
There is no restriction | limiting in particular as crude copper powder used for the manufacturing method of the said copper solution, Although it can select suitably according to the objective, What was pulverized as follows is preferable.
−粗銅−
前記粗銅の原料としては、特に制限はなく、例えば鉱山から掘り出した銅品位０．５％〜２．０％の銅鉱石を選鉱して銅品位２０％〜４０％に高めた銅精鉱を用いることが一般的であるが、本発明においては、廃プリント基板、廃電子部品、及び廃電気部品から選択されるリサイクル原料を用いることが、資源の有効利用を図ることができる点から好ましい。
-Crude copper-
There is no restriction | limiting in particular as a raw material of the said rough copper, For example, the copper concentrate which selected the copper ore of the copper grade 0.5%-2.0% excavated from the mine, and raised it to the copper grade 20%-40% is used. However, in the present invention, it is preferable to use a recycled material selected from a waste printed circuit board, a waste electronic component, and a waste electrical component from the viewpoint of effective utilization of resources.
前記リサイクル原料は、粉砕、篩い分けし、これを比重差、磁力、渦電流選別、静電選別により、銅及び貴金属等を濃縮回収して銅濃縮物とし、これを乾式製錬によって、粗銅の製造を行う。
前記粗銅中には、Ｃｕ以外にも、通常、Ａｓ、Ｎｉ、Ｐｂ、Ｓｎ、Ｚｎ、Ｆｅ、Ｓｂ、Ｂｉ、Ｓ、Ｔｅ、Ｓｅ、Ａｕ、Ａｇ、Ｐｔ、Ｐｄなどが微量に含まれており、これらの中でも、Ａｕ、Ａｇ、Ｐｔ、Ｐｄの貴金属を多く含むものが特に好ましい。
The recycled material is pulverized and sieved, and this is concentrated and recovered into copper concentrate by copper, precious metal, etc. by specific gravity difference, magnetic force, eddy current sorting and electrostatic sorting. Manufacture.
In addition to Cu, the crude copper usually contains trace amounts of As, Ni, Pb, Sn, Zn, Fe, Sb, Bi, S, Te, Se, Au, Ag, Pt, Pd and the like. Among these, those containing a large amount of noble metals such as Au, Ag, Pt, and Pd are particularly preferable.
前記粗銅中における銅濃度は、９３質量％〜９５質量％であることが好ましい。本発明の銅溶解液の浄液方法により製造された銅電解液を用いれば、このように銅濃度が低い粗銅からでも、高純度な精製銅を効率よく得ることができる。 The copper concentration in the crude copper is preferably 93% by mass to 95% by mass. If the copper electrolyte solution manufactured by the copper solution purification method of the present invention is used, highly purified copper can be efficiently obtained even from crude copper having a low copper concentration.
＜粉体化処理＞
前記粉体化処理としては、特に制限はなく、目的に応じて適宜選択することができ、例えば湿式還元法、気相還元法、アトマイズ法などが挙げられる。これらの中でも、低コストで大量に生産できる点からアトマイズ法が特に好ましい。
<Powdering process>
There is no restriction | limiting in particular as said powdering process, According to the objective, it can select suitably, For example, a wet reduction method, a vapor phase reduction method, an atomization method etc. are mentioned. Among these, the atomizing method is particularly preferable because it can be produced in large quantities at a low cost.
前記アトマイズ法とは、溶融金属流に高圧のガス又は水を粉砕媒体として噴射して金属流を粉砕し、冷却し、凝固させて粗銅粉を製造する方法である。
前記粉砕媒体にガスを適用するガスアトマイズ法では、得られる粗銅粉は球形状を呈しており、不活性ガスを用いることで酸素含有量の低い粗銅粉を製造することができるが、粒径が比較的粗くなってしまう。これは、前記ガスアトマイズ法では溶融した銅の冷却速度が低いことによる。
The atomizing method is a method of producing a crude copper powder by injecting a high-pressure gas or water as a grinding medium into a molten metal stream, grinding the metal stream, cooling and solidifying it.
In the gas atomization method in which gas is applied to the grinding medium, the obtained crude copper powder has a spherical shape, and it is possible to produce crude copper powder with a low oxygen content by using an inert gas, but the particle size is compared. It becomes rough. This is because the cooling rate of molten copper is low in the gas atomization method.
これに対し、前記粉砕媒体に水を用いる水アトマイズ法は、ガスと同じ流速でせん断しても、水の質量がガスよりも重いことより、せん断エネルギーが大きく、粒径の小さなものが製造できる。また、冷却速度を高くすることができ、粒形状は不定形で表面に凹凸の多い粉体が製造されることが多い。また、上記の理由から、表面積の大きい粒子となるため、溶融金属の冷却時に発生する水蒸気と雰囲気中の酸素の影響で、酸素含有量が比較的高い粉体が製造される。 In contrast, the water atomization method using water as the pulverizing medium can produce a product having a large shear energy and a small particle size because the mass of water is heavier than the gas even when shearing at the same flow rate as the gas. . In addition, the cooling rate can be increased, and a powder having an irregular grain shape and many irregularities on the surface is often produced. Moreover, since it becomes a particle | grain with a large surface area for said reason, the powder with comparatively high oxygen content is manufactured under the influence of the water vapor | steam which generate | occur | produces at the time of molten metal cooling, and the oxygen in atmosphere.
本発明においては、前記水アトマイズ法では、溶融金属流を略中心に流し、水ジェットをその周囲から逆円錐形状となるよう噴射し、又は溶融金属流に帯状の水ジェットを対向させたＶ字形状となるように噴射して、この水ジェットの収束する点（線）又はその近傍で溶融金属を粉砕している。アトマイズにおいて、溶湯と水ジェットとのなす角度は、粉砕力に大きく影響し、また、溶融金属（溶湯）の跳ね返り現象にも大きく影響するため、溶融金属流に帯状の水ジェットを対向させたＶ字形状となるように噴射する方が、噴射角度の調製などの自由度の点では好ましい。 In the present invention, in the water atomization method, a molten metal flow is caused to flow substantially in the center, and a water jet is jetted from its periphery so as to have an inverted conical shape, or a V-shaped water jet is opposed to the molten metal flow. The molten metal is crushed at the point (line) where the water jet converges or in the vicinity thereof by injecting it into a shape. In atomization, the angle between the molten metal and the water jet greatly affects the crushing force and also greatly affects the rebound phenomenon of the molten metal (molten metal). It is more preferable to inject so that it may become a letter shape from the point of freedom, such as adjustment of an injection angle.
ここで、前記アトマイズ処理に使用するアトマイズ装置の一例としては、図２に示すように、溶融した粗銅を保持し、傾転できる保持炉から樋１６をつたって溶融した溶融銅流を受け、貯留するタンディッシュ１０と、該タンディッシュ１０の底部のノズル１１より溶融銅流を流下して、該流下している溶融銅流に対し高圧の水又は空気を吐出して溶融銅流を粉状化する噴霧部１２と、該噴霧部１２の下方にあって、粉状化した粗銅粉を冷却し、貯蔵し、搬出する貯蔵部１３とを有している。図２中、１４はストッパー、１５はタンディッシュ１０内の溶融銅を保温するためのバーナー、１７は邪魔板棒を表す。
また別の装置の例としては、ルツボを有する炉内のルツボ底部に溶湯ノズル孔を空け、上述と同様にノズルより出湯してもよい。
Here, as an example of the atomizing apparatus used for the atomizing process, as shown in FIG. 2, the molten copper flow is retained by holding a molten iron flow from a holding furnace capable of holding and tilting molten copper. The molten copper flow is made to flow down from the tundish 10 and the nozzle 11 at the bottom of the tundish 10, and the molten copper flow is pulverized by discharging high-pressure water or air to the flowing molten copper flow. The spraying part 12 to be used, and the storage part 13 which is below the spraying part 12 and cools, stores and carries out the powdered crude copper powder. In FIG. 2, 14 is a stopper, 15 is a burner for keeping the molten copper in the tundish 10 warm, and 17 is a baffle plate bar.
As another example of the apparatus, a molten metal nozzle hole may be formed at the bottom of the crucible in the furnace having the crucible, and the hot water may be discharged from the nozzle in the same manner as described above.
更に、水アトマイズ法について詳細に説明する。まず、粗銅を溶解しこの溶融粗銅をタンディッシュ１０の底部ノズル１１から流下して溶融銅流の流れを形成し、この溶融銅流の流れに対し水ジェットを噴射する。この溶融銅の温度は銅の溶融温度（約１０８３℃）に対して５０℃以上高温とすることが好ましく、１５０℃以上高温とするのがより好ましい。前記溶融温度が、１５０℃未満であると、不純物の多い溶融銅流の粘度が高すぎてスムースに流れができないことがある。また、タンディッシュ１０から溶融銅流を流下する際には、その底部にノズル１１を設け、該ノズル１１より溶融銅流を流下させるのが一般的であるが、前記ノズル径は直径０．５ｍｍ〜３０ｍｍが好ましく、０．５ｍｍ〜２０ｍｍがより好ましく、３ｍｍ〜１５ｍｍが更に好ましく、３ｍｍ〜１０ｍｍが特に好ましい。また、ノズル形状は円形でなくてもよいが、その面積は前記円形の場合の面積と同等の範囲であることが好ましい。この範囲を外れると溶融銅流の流量の調節が困難となると共に、溶融銅流の詰まりが生じるおそれがある。また、前記ノズル径が大きすぎると微細な粒系の粉末を製造するのが困難となるからである。
また、ノズルは複数あってもよく、前記溶融銅流量は１ノズルあたり１０ｋｇ／ｍｉｎ〜６０ｋｇ／ｍｉｎが好ましく、２０ｋｇ／ｍｉｎ〜５０ｋｇ／ｍｉｎがより好ましい。
溶融銅の噴射流速（圧力）は、吐出水流速を決める要因で、吐出水流の流速としては、１００ｍ／ｓ以上が好ましく、２００ｍ／ｓ以上がより好ましい。
水量は、水／溶体比で２以上が好ましく、３以上がより好ましく、４以上が更に好ましい。前記水／溶体比が不十分では、十分な粉砕効果が得られず、粗粉となりやすい。また、水溶体比を高くすることで、発生する水蒸気量を低減できる。
総溶体流量は、上記関係のバランスをとれば出湯量については、特に制限はなく、目的に応じて適宜選択することができ、例えば６０ｋｇ／ｍｉｎ〜８０ｋｇ／ｍｉｎ程度が好ましい。
Further, the water atomization method will be described in detail. First, the crude copper is melted, and the molten crude copper is flowed down from the bottom nozzle 11 of the tundish 10 to form a molten copper flow, and a water jet is injected into the molten copper flow. The temperature of the molten copper is preferably 50 ° C. or higher and more preferably 150 ° C. or higher with respect to the copper melting temperature (about 1083 ° C.). When the melting temperature is less than 150 ° C., the viscosity of the molten copper stream containing many impurities may be too high to smoothly flow. In addition, when the molten copper flow is caused to flow down from the tundish 10, a nozzle 11 is generally provided at the bottom thereof, and the molten copper flow is caused to flow down from the nozzle 11, but the nozzle diameter is 0.5 mm in diameter. -30 mm is preferable, 0.5 mm to 20 mm is more preferable, 3 mm to 15 mm is still more preferable, and 3 mm to 10 mm is particularly preferable. Further, the nozzle shape may not be circular, but the area thereof is preferably in a range equivalent to the area in the case of the circular shape. Outside this range, it becomes difficult to adjust the flow rate of the molten copper flow, and the molten copper flow may be clogged. Further, if the nozzle diameter is too large, it is difficult to produce fine granular powder.
Moreover, there may be a plurality of nozzles, and the molten copper flow rate is preferably 10 kg / min to 60 kg / min, more preferably 20 kg / min to 50 kg / min per nozzle.
The molten copper injection flow rate (pressure) is a factor that determines the discharge water flow rate, and the flow rate of the discharge water flow is preferably 100 m / s or more, and more preferably 200 m / s or more.
The amount of water is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more in terms of water / solution ratio. If the water / solution ratio is insufficient, a sufficient pulverization effect cannot be obtained, and a coarse powder tends to be obtained. Moreover, the amount of water vapor | steam generated can be reduced by making water solution ratio high.
The total solution flow rate is not particularly limited as long as the above relationship is balanced, and can be appropriately selected according to the purpose, and is preferably about 60 kg / min to 80 kg / min, for example.
前記水ジェットの噴射条件として、その水圧は１０ＭＰａ〜１００ＭＰａが好ましく、２０ＭＰａ〜５０ＭＰａがより好ましい。前記水圧が１０ＭＰａ未満であると、粗銅粉の粒径を微細化することができなくなることがあり、前記水圧は１０ＭＰａ以上であれば粒径の微細化、表面の平滑化が可能となるが、水圧が１００ＭＰａを超えるような高圧では噴射させる装置が大掛かりとなり現実的ではなくなる。また、前記水圧を上記範囲とすることに加え、水流量は５０Ｌ／ｍｉｎ〜１，０００Ｌ／ｍｉｎが好ましく、３００Ｌ／ｍｉｎ〜６００Ｌ／ｍｉｎがより好ましい。前記水流量が、５０Ｌ／ｍｉｎ未満であると、発生水蒸気の巻き上げが生じて、粗銅粉の酸化が促進され酸素含有量が大きくなることがあり、１，０００Ｌ／ｍｉｎを超えると、粉末の過冷却が生じると共に装置的にも困難となる。 As the injection conditions of the water jet, the water pressure is preferably 10 MPa to 100 MPa, more preferably 20 MPa to 50 MPa. If the water pressure is less than 10 MPa, the particle size of the coarse copper powder may not be refined, and if the water pressure is 10 MPa or more, the particle size can be refined and the surface smoothed. At a high pressure such that the water pressure exceeds 100 MPa, the spraying apparatus becomes large and unrealistic. Moreover, in addition to making the said water pressure into the said range, 50 L / min-1,000 L / min are preferable, and 300 L / min-600 L / min are more preferable. When the water flow rate is less than 50 L / min, the generated water vapor is wound up, and the oxidation of the crude copper powder is promoted to increase the oxygen content. Cooling occurs and the apparatus becomes difficult.
噴霧部１２の噴射ノズルから噴射する水ジェット流の形状としては、扇状かつ平面状に噴射され、図３に示すように３個の噴射ノズル１００，１００，１００を用いた逆３角錐形状、或いは図４に示すように４個の噴射ノズル１００，１００，１００，１００を用いた逆４角錐形状が好ましい。
図３では、３個の噴射ノズル１００，１００，１００より３方向から水を扇状かつ平面状に噴射し、水の噴射で逆３角錐状の形状を形成し、その略中心部に溶融銅流１０１を流下して、粉砕する。
図４では、４個の噴射ノズル１００，１００，１００，１００より４方向から水を扇状かつ平面状に噴射し、水の噴射で逆４角錐状の形状を形成し、その略中心部に溶融銅流１０１を流下して、粉砕する。
また、図５に示すように、噴射ノズル１００から噴出する水ジェット流の扇状の頂角θは１０°〜３０°が好ましく、１５°〜２５°がより好ましい。前記頂角θが、１０°未満であると、溶融銅流が水ジェット流から外れる場合があり、ある程度の角度で広げて、溶融銅流と水ジェットが確実に衝突する必要がある。また、その角度が広すぎても、水ジェット流が無駄に広がるため、有効でない水流が存在してしまう。
As the shape of the water jet flow ejected from the spray nozzle of the spraying section 12, it is sprayed in a fan shape and a planar shape, and as shown in FIG. As shown in FIG. 4, an inverted quadrangular pyramid shape using four injection nozzles 100, 100, 100, 100 is preferable.
In FIG. 3, water is sprayed in three directions from three spray nozzles 100, 100, 100 in a fan shape and in a planar shape, and an inverted trigonal pyramid shape is formed by the water spray. Flow down 101 and grind.
In FIG. 4, water is sprayed from four directions from four spray nozzles 100, 100, 100, 100 in a fan-like and flat shape, and an inverted quadrangular pyramid shape is formed by the water spray, and is melted at the substantially central portion thereof. The copper stream 101 flows down and is crushed.
As shown in FIG. 5, the fan-like apex angle θ of the water jet flow ejected from the ejection nozzle 100 is preferably 10 ° to 30 °, and more preferably 15 ° to 25 °. When the apex angle θ is less than 10 °, the molten copper flow may deviate from the water jet flow, and it is necessary to spread the molten copper flow at a certain angle so that the molten copper flow and the water jet collide with each other. Moreover, even if the angle is too wide, the water jet flow unnecessarily spreads, so that there is an ineffective water flow.
前記粉体化処理により得られる粗銅粉の粒度分布において、粒径２５０μｍ以下の粗銅粉の質量割合は９０％以上が好ましく、粒径１０６μｍ以下の粗銅粉の質量割合が９０％以上であることがより好ましい。前記粒径が大きすぎると、後述する銅粉溶解工程において粗銅粉の溶解速度が遅くなって効率が悪くなることがある。 In the particle size distribution of the crude copper powder obtained by the powdering treatment, the mass ratio of the coarse copper powder having a particle size of 250 μm or less is preferably 90% or more, and the mass ratio of the crude copper powder having a particle size of 106 μm or less is 90% or more. More preferred. If the particle size is too large, the dissolution rate of the coarse copper powder may be slowed in the copper powder dissolving step described later, resulting in poor efficiency.
−溶解処理−
次に、粉体化処理により得られる粗銅粉を、硫酸を含む液で溶解する。該粗銅粉の溶解方法としては、前記粗銅粉を溶解するための溶解槽と、該溶解槽で溶解し残った粗銅粉を沈殿させて、該沈殿物を液と共に前記溶解槽に戻す沈殿槽とを用いる。
前記沈殿槽においては、攪拌機を有さない、即ち攪拌を行わないことが、残粗銅粉は送液後にすぐに沈降始め、沈殿槽の底部周辺に堆積させることができる点で好ましい。
更に前記沈殿させた粗銅粉及び液は、溶解槽の底部近傍から戻すことが好ましい。
-Dissolution treatment-
Next, the crude copper powder obtained by pulverization is dissolved with a liquid containing sulfuric acid. As the method for dissolving the crude copper powder, a dissolution tank for dissolving the crude copper powder, a precipitation tank for precipitating the crude copper powder remaining in the dissolution tank and returning the precipitate to the dissolution tank together with the liquid, Is used.
In the settling tank, it is preferable not to have a stirrer, that is, not to perform stirring, because the remaining crude copper powder starts to settle immediately after feeding and can be deposited around the bottom of the settling tank.
Furthermore, it is preferable to return the precipitated coarse copper powder and liquid from the vicinity of the bottom of the dissolution tank.
ここで、図６に示すように、銅溶解液を作製する溶解槽３０は、銅溶解液を貯留する溶解槽本体３１と、溶解槽本体の内側には、邪魔板３２が配置され、銅溶解液の攪拌のための攪拌機３３が配置されている。攪拌機３３は、回転数の制御可能とし、タービン羽４枚が１段となっている。また、貯留している液の温度の昇降、恒温制御を可能としている。溶解槽には、側壁に液の一部を流出し、沈殿槽３５に送液する配管３４がある。沈殿槽３５は、溶解槽３０で溶解し残った残粗銅粉が液とともに流入され、残粗銅粉を沈降させ、溶解槽３０に戻すポンプ３６を備えてある。図６中、３７は粗銅粉供給ホッパ、３８は酸化剤供給としてのエアー噴出器を表す。 Here, as shown in FIG. 6, the dissolution tank 30 for preparing the copper dissolution liquid has a dissolution tank body 31 for storing the copper dissolution liquid, and a baffle plate 32 is disposed inside the dissolution tank body, so that the copper dissolution is performed. A stirrer 33 for stirring the liquid is disposed. The stirrer 33 can control the number of rotations, and four turbine blades are in one stage. In addition, the temperature of the stored liquid can be raised and lowered and controlled at a constant temperature. In the dissolution tank, there is a pipe 34 through which a part of the liquid flows out to the side wall and is sent to the precipitation tank 35. The settling tank 35 is provided with a pump 36 into which the remaining coarse copper powder that has been dissolved in the dissolving tank 30 flows in together with the liquid, precipitates the remaining coarse copper powder, and returns it to the dissolving tank 30. In FIG. 6, reference numeral 37 denotes a coarse copper powder supply hopper, and 38 denotes an air ejector as an oxidant supply.
なお、溶解を開始から数分間後には、溶解途中である残銅粉が浮遊してくるため、これを液とともに沈殿槽３５に送液する。そのため、配管３４の溶解槽３０側の開口は、銅溶解液液面付近が好ましい。沈殿槽３５では、攪拌機がないため残粗銅粉は送液後にすぐに沈降始め、沈殿槽の底部周辺に堆積する。これを底部より液とともに抜き出し、ポンプ３６を介して溶解槽３０に液と残粗銅粉を投入する。この際、溶解槽３０の底部に戻すことが好ましい。 In addition, after several minutes from the start of dissolution, the remaining copper powder that is in the middle of dissolution floats, and is sent to the precipitation tank 35 together with the liquid. Therefore, the opening on the side of the dissolution tank 30 of the pipe 34 is preferably near the copper solution liquid surface. In the settling tank 35, since there is no stirrer, the remaining coarse copper powder begins to settle immediately after the liquid is fed and is deposited around the bottom of the settling tank. This is extracted together with the liquid from the bottom, and the liquid and the remaining coarse copper powder are put into the dissolution tank 30 via the pump 36. At this time, it is preferable to return to the bottom of the dissolution tank 30.
図６に示すように、溶解槽３０に沈殿槽３５を配置し、この沈殿槽３５にて沈殿させた粗銅粉を溶解槽３０に送り、再度溶解反応をさせる。このように未溶解の粗銅粉を巡回させながら粗銅粉を溶解すると銅の溶解効率が顕著に向上し、溶解時間の短縮が可能となり、製造コストの大幅な削減が可能となる。 As shown in FIG. 6, a precipitation tank 35 is disposed in the dissolution tank 30, and the crude copper powder precipitated in the precipitation tank 35 is sent to the dissolution tank 30 to cause a dissolution reaction again. When the crude copper powder is dissolved while circulating the undissolved crude copper powder in this manner, the copper dissolution efficiency is remarkably improved, the dissolution time can be shortened, and the manufacturing cost can be greatly reduced.
以上説明した銅溶解液の製造方法により、銅濃度が、５０ｇ／Ｌ〜１５０ｇ／Ｌである銅溶解液を作製することができる。前記銅濃度は７０ｇ／Ｌ〜１４０ｇ／Ｌがより好ましい。 By the copper solution manufacturing method described above, a copper solution having a copper concentration of 50 g / L to 150 g / L can be produced. The copper concentration is more preferably 70 g / L to 140 g / L.
次に、本発明の銅溶解液の浄液方法においては、上述のような工程で製造された銅溶解液に、粗銅粉又は酸化剤を添加し、一次残渣を濾別した濾液に粗銅粉を添加し、遊離硫酸濃度を下げ、銅濃度を調整すると共に、濾液中の不純物を除去して銅電解液を調製する。該酸化剤としては、例えば酸素、過酸化水素などが挙げられる。前記不純物としては、Ａｓ、Ｓｂ、Ｓｎなどが挙げられる。
前記浄液方法により調製された銅電解液は、銅濃度が７０ｇ／Ｌ〜１００ｇ／Ｌ、遊離硫酸濃度が５ｇ／Ｌ以下が好ましく、特に１ｇ／Ｌ以下の硫酸銅溶液であり、液温は１０℃〜４０℃に調整されている。
Next, in the copper solution purification method of the present invention, crude copper powder or oxidant is added to the copper solution produced in the process as described above, and the crude copper powder is added to the filtrate obtained by filtering the primary residue. Add and lower the free sulfuric acid concentration to adjust the copper concentration, and remove the impurities in the filtrate to prepare a copper electrolyte. Examples of the oxidizing agent include oxygen and hydrogen peroxide. Examples of the impurities include As, Sb, and Sn.
The copper electrolyte prepared by the above liquid purification method is preferably a copper sulfate solution having a copper concentration of 70 g / L to 100 g / L and a free sulfuric acid concentration of 5 g / L or less, particularly 1 g / L or less. It is adjusted to 10 ° C to 40 ° C.
前記浄液方法は、前記一次浸出工程の濾液である前記銅溶解液の遊離硫酸濃度を下げ、銅濃度を電解用に調整した銅電解液を調製するとともに、銅溶解液中の不純物を除去する工程であり、電解工程の前に実施することが好ましい。
前記浄液工程においては、銅溶解中の不純物（例えばＡｓ、Ｓｂ、Ｓｎ）を低減する。例えば、銅溶解液に、粗銅粉を添加し、空気を液中に吹き込み、攪拌しながら銅溶解中に粗銅粉を溶解して遊離硫酸濃度を低減した。反応後は濾過し、濾液の銅濃度を電解用に調整すれば銅電解用の電解液が得られる。このように粗銅粉を用いることにより、特に銅電解における阻害元素である砒素の除去が可能となり、硫化水素等の新たな薬剤を用いることもないのでコストの増大を抑制することができる。
The said liquid purification method lowers the free sulfuric acid concentration of the said copper solution which is the filtrate of the said primary leaching process, and prepares the copper electrolyte which adjusted the copper concentration for electrolysis, and removes the impurity in a copper solution. It is a process and is preferably performed before the electrolysis process.
In the liquid purification step, impurities (for example, As, Sb, Sn) during copper dissolution are reduced. For example, crude copper powder was added to a copper solution, air was blown into the liquid, and the crude copper powder was dissolved during copper dissolution while stirring to reduce the free sulfuric acid concentration. After the reaction, the solution is filtered, and the copper concentration of the filtrate is adjusted for electrolysis to obtain an electrolytic solution for copper electrolysis. By using the crude copper powder in this manner, it is possible to remove arsenic, which is an inhibitory element particularly in copper electrolysis, and it is possible to suppress an increase in cost because a new agent such as hydrogen sulfide is not used.
（銅の製造方法）
以下、本発明の銅の製造方法の一実施形態として、上述の本発明の銅溶解液の浄液方法を浄液工程として用いた銅の製造方法について、図７を参照して説明する。
(Copper production method)
Hereinafter, as an embodiment of the copper production method of the present invention, a copper production method using the above-described copper solution purification method of the present invention as a liquid purification step will be described with reference to FIG.
本発明の銅の製造方法は、粉体化工程と、銅粉溶解工程と、濾過工程と、浄液工程と、電解工程とを含み、更に必要に応じて、脱銀置換工程、二次浸出工程、浄液工程等のその他の工程を含んでもよい。なお、銅粉溶解工程と、濾過工程とを併せて一次浸出工程と称することもある。
前記銅の製造方法によれば、貴金属を早期に回収しその有効利用が図れ、不純物を電解前に除去することができ、また、粗銅粉を用いることにより銅の溶解効率が向上し、硫酸を繰り返し使用でき、高品位な精製銅を効率的に製造できる。
The method for producing copper of the present invention includes a powdering step, a copper powder dissolving step, a filtration step, a liquid purification step, and an electrolysis step, and if necessary, a desilvering substitution step, a secondary leaching. You may include other processes, such as a process and a liquid purification process. In addition, a copper powder melt | dissolution process and a filtration process may be collectively called a primary leaching process.
According to the copper production method, the precious metal can be recovered early and effectively used, impurities can be removed before electrolysis, and the copper dissolution efficiency can be improved by using the crude copper powder, and sulfuric acid can be used. It can be used repeatedly, and high-quality purified copper can be produced efficiently.
＜粉体化工程＞
前記粉体化工程は、本発明の銅溶解液の浄液方法における粉体化処理と同様であり、この工程により粗銅粉が得られる。
<Powdering process>
The said powdering process is the same as the powdering process in the liquid purification method of the copper solution of this invention, and a rough copper powder is obtained by this process.
＜一次浸出工程＞
前記一次浸出工程は、銅粉溶解工程と、濾過工程とを含み、必要に応じて脱銀置換工程を含んでいてもよい。
<Primary leaching process>
The primary leaching step includes a copper powder dissolution step and a filtration step, and may include a desilvering replacement step as necessary.
−銅粉溶解工程−
前記銅溶解工程は、本発明の銅溶解液の浄液方法の溶解処理と同様であり、この工程により銅溶解液が作製される。
-Copper powder dissolution process-
The copper dissolution step is the same as the dissolution treatment of the copper solution purification method of the present invention, and a copper solution is produced by this step.
−濾過工程−
前記濾過工程は、銅粉溶解槽の銅粉溶解スラリーを含む銅溶解液を、濾過する工程である。ここで銅が溶け込んだ銅溶解液に溶けず、沈殿物として残ったものを濾過し、一次残渣を得る。
-Filtration process-
The said filtration process is a process of filtering the copper solution containing the copper powder melt | dissolution slurry of a copper powder melt | dissolution tank. Here, what is not dissolved in the copper solution in which copper is dissolved but remains as a precipitate is filtered to obtain a primary residue.
−脱銀置換工程−
前記銅粉溶解工程と前記濾過工程の間に、脱銀置換工程を含んでいてもよい。この脱銀置換工程は、銅溶解槽の銅粉溶解スラリーを含む溶液を、銅粉溶解槽から脱銀置換槽に送液し、この脱銀置換槽の中で処理する工程である。
ここでは、銅が溶け込んだ銅溶解液中に、微量に溶解している銀、及びその他貴金属を、銅粉溶解スラリー中にある未溶解銅粉で、セメンテーションして、溶解分の銀、貴金属を固体化する工程となる。銅粉溶解槽で温度をかけて、酸化すると、銅以外に銀等が微量に溶け出すためそれを戻す役目もある。脱銀置換槽は、低攪拌のみで、酸素の吹き込みを行わず、一定の滞留時間でセメンテーションを行うものである。その後、前記セメンテーションによる沈殿物を濾過して貴金属を含む一次残渣を得る。
前記濾過の方法としては、特に制限はなく、目的に応じて適宜選択することができるが、例えばフィルタープレス、減圧濾過などが挙げられる。
-Desilvering substitution step-
A desilvering substitution step may be included between the copper powder dissolution step and the filtration step. This desilvering and replacing step is a step in which a solution containing the copper powder dissolving slurry in the copper dissolving tank is fed from the copper powder dissolving tank to the desilvering and replacing tank and processed in the desilvering and replacing tank.
Here, a small amount of silver and other precious metals dissolved in the copper solution in which copper is dissolved are cemented with undissolved copper powder in the copper powder dissolving slurry, and the dissolved silver and precious metal It becomes the process of solidifying. When oxidized by applying a temperature in a copper powder dissolution tank, silver and the like dissolve in a very small amount in addition to copper, and have the role of returning it. The desilvering / replacement tank performs cementation with a constant residence time without blowing oxygen with only low stirring. Thereafter, the precipitate resulting from the cementation is filtered to obtain a primary residue containing a noble metal.
The filtration method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a filter press and vacuum filtration.
なお、後述する二次浸出槽（残渣溶解槽）の濾液、及び浄液溶解槽の濾液には、大量の銀が溶け出しているため、これらの濾液は脱銀置換槽に入れ、上記銅粉溶解スラリーとともに、セメンテーションを行います。また、溶解した銀は電解では銅よりも先に電着され、電気銅品位悪化の原因になるので、一次浸出工程、及び二次浸出工程で残渣として取り出し、後述する貴金属回収工程で回収する。 Since a large amount of silver is dissolved in the filtrate of the secondary leaching tank (residue dissolution tank) and the filtrate of the purification liquid dissolution tank, which will be described later, these filtrates are put in a desilvering and replacement tank, and the above copper powder Perform cementation with the dissolved slurry. In addition, since the dissolved silver is electrodeposited prior to copper in electrolysis and causes deterioration of the quality of electrolytic copper, it is taken out as a residue in the primary leaching process and the secondary leaching process, and collected in a noble metal recovery process described later.
＜二次浸出工程（残渣溶解工程）＞
前記二次浸出工程は、前記一次残渣を使用済み銅電解液で浸出し、該浸出液に酸化剤を添加し、一次残渣より貴金属濃度を上げた二次残渣を得る工程であり、一次残渣中の貴金属濃度を上げるために実施される。
即ち、前記一次浸出工程の一次残渣を前記使用済み銅溶解液中に浸漬し、溶解するが、更に二次残渣（不溶性沈殿）が残存する。これを濾過し、二次残渣（不溶性沈殿）を除去する。このとき、二次残渣（不溶性沈殿）中の貴金属濃度は一次残渣よりも高くなっている。
前記酸化剤としては、例えば酸素ガス、空気、過酸化水素、などが挙げられる。
<Secondary leaching process (residue dissolution process)>
The secondary leaching step is a step of leaching the primary residue with a used copper electrolyte solution, adding an oxidizing agent to the leaching solution, and obtaining a secondary residue having a higher precious metal concentration than the primary residue. Performed to increase the concentration of noble metals.
That is, the primary residue of the primary leaching step is immersed and dissolved in the used copper solution, but a secondary residue (insoluble precipitate) remains. This is filtered to remove secondary residues (insoluble precipitate). At this time, the concentration of noble metal in the secondary residue (insoluble precipitate) is higher than that of the primary residue.
Examples of the oxidizing agent include oxygen gas, air, and hydrogen peroxide.
前記二次浸出工程では、前記一次浸出工程からの一次残渣（溶解残渣）を後述の電解工程で使用済みとなった銅電解液（電解尾液）を用いて浸出することが好ましい。この電解尾液は、電解において銅等の金属イオンが液中から採取されているため、遊離硫酸濃度が高く、浸出性が強い酸である。一次残渣中の銅は、ほとんど液中に浸出されるが、硫酸に溶けにくい貴金属類は二次残渣中に移行される。二次残渣は、濾過等により得られ、貴金属回収工程の原料として使用される。 In the secondary leaching step, the primary residue (dissolved residue) from the primary leaching step is preferably leached using a copper electrolyte solution (electrolytic tail solution) that has been used in an electrolysis step described later. This electrolytic tail solution is an acid having a high concentration of free sulfuric acid and a strong leachability since metal ions such as copper are collected from the solution during electrolysis. Most of the copper in the primary residue is leached into the liquid, but noble metals that are hardly soluble in sulfuric acid are transferred into the secondary residue. The secondary residue is obtained by filtration or the like and used as a raw material for the precious metal recovery step.
＜貴金属回収工程＞
前記貴金属回収工程は、二次残渣から貴金属を回収する工程である。
前記貴金属としては、銀、金、白金、パラジウム、ロジウム、ルテニウムなどが挙げられる。
前記二次残渣から貴金属を回収する方法としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば電解精製、電解採取などが挙げられる。
<Precious metal recovery process>
The noble metal recovery step is a step of recovering noble metal from the secondary residue.
Examples of the noble metal include silver, gold, platinum, palladium, rhodium, and ruthenium.
There is no restriction | limiting in particular as a method of collect | recovering noble metals from the said secondary residue, Although it can select suitably according to the objective, For example, electrolytic purification, electrowinning, etc. are mentioned.
＜浄液工程＞
前記浄液工程は、本発明の銅溶解液の浄液方法と同様であり、この工程により銅電解液が作製される。
<Purification process>
The said liquid purification process is the same as the liquid purification method of the copper solution of this invention, and a copper electrolyte solution is produced according to this process.
＜電解工程＞
前記電解工程は、前記一次浸出工程又は前記浄液工程において得られた銅溶解液（濾液）を、電解用に調整された銅電解液を電解して電気銅を得る工程である。
前記一次浸出工程又は前記浄液工程の銅濃度を例えば使用済銅電解液により調整して銅電解液とする。銅電解液は、銅濃度が７０ｇ／Ｌ〜１００ｇ／Ｌ、遊離硫酸濃度が５ｇ／Ｌ以下が好ましく、特に１ｇ／Ｌ以下の硫酸銅溶液であり、液温は１０℃〜４０℃に調整されている。
前記電解工程における電解条件としては、特に制限はなく、目的に応じて適宜選択することができるが、以下の通りであることが好ましい。
〔電解条件〕
・電流密度：２０Ａ／ｍ２〜７００Ａ／ｍ２が好ましく、３０Ａ／ｍ２〜４００Ａ／ｍ２がより好ましい。
・浴電圧：０．５Ｖ〜３Ｖ
・浴温度：３０℃〜８０℃が好ましく、４０℃〜７０℃がより好ましい。
アノードとしては、例えばＰｂ、Ｐｂ合金などが用いられる。
カソードとしては、例えば銅、ステンレスなどが用いられる。
<Electrolysis process>
The electrolysis step is a step of obtaining electrolytic copper by electrolyzing a copper solution (filtrate) obtained in the primary leaching step or the liquid purification step with a copper electrolyte adjusted for electrolysis.
The copper concentration in the primary leaching step or the liquid purification step is adjusted with, for example, a used copper electrolytic solution to obtain a copper electrolytic solution. The copper electrolytic solution is preferably a copper sulfate solution having a copper concentration of 70 g / L to 100 g / L and a free sulfuric acid concentration of 5 g / L or less, particularly 1 g / L or less, and the liquid temperature is adjusted to 10 ° C. to 40 ° C. ing.
There is no restriction | limiting in particular as electrolysis conditions in the said electrolysis process, Although it can select suitably according to the objective, It is preferable as follows.
[Electrolysis conditions]
Current density: Preferably 20A / m 2 ~700A / m 2 , 30A / m 2 ~400A / m 2 is more preferable.
・ Bath voltage: 0.5V-3V
-Bath temperature: 30 to 80 degreeC is preferable and 40 to 70 degreeC is more preferable.
As the anode, for example, Pb, Pb alloy or the like is used.
For example, copper or stainless steel is used as the cathode.
なお、液温は高いほど電力原単位が低下できるので高い方が好ましいが、表面を平滑化させる目的で添加するニカワなどの分解速度が大きくなり、設備上の温度制約、作業雰囲気、加熱コストなどの理由から、上限を設定することが好ましい。 In addition, the higher the liquid temperature, the lower the power intensity, which is preferable. However, the decomposition rate of glue added for the purpose of smoothing the surface increases, the temperature constraint on the equipment, working atmosphere, heating cost, etc. For this reason, it is preferable to set an upper limit.
前記電解工程としては、具体的には、図８に示すように、電解槽４内の銅電解液３中で、鉛系アノード１から高純度の銅板からなるカソード２に整流器を経て直流電流を流すことにより、アノード１で水が電気分解して電子がカソード２に移行し、カソード板の表面に電気銅（純銅）として析出するものである。
前記電解工程においては、従来に比べて、アノードが不働態化せず、また、アノードから発生するスライムの影響を受け難く、電気銅品位が向上する。
Specifically, as shown in FIG. 8, in the electrolytic process, the electrolysis process is performed by applying a direct current from a lead-based anode 1 to a cathode 2 made of a high-purity copper plate through a rectifier in a copper electrolyte 3 in an electrolytic cell 4. By flowing, water is electrolyzed at the anode 1, electrons move to the cathode 2, and deposit as electrolytic copper (pure copper) on the surface of the cathode plate.
In the electrolysis step, the anode is not passivated as compared with the prior art, and is less susceptible to the slime generated from the anode, so that the quality of electrolytic copper is improved.
前記銅の製造方法により製造された銅は、従来に比べて電解液に含まれる不純物（貴金属を含む）が少ないために銅品位の高い高純度なものであり、電子部品材料、電子機器材料、ＬＳＩ用配線、電線等の各種分野に好適に用いられる。 The copper produced by the copper production method is high-purity with high copper quality because there are fewer impurities (including noble metals) contained in the electrolyte than in the past, and electronic component materials, electronic equipment materials, It is suitably used in various fields such as LSI wiring and electric wires.
以下、本発明の実施例について説明するが、本発明はこれらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
＜銅溶解液の製造＞
−粗銅の調製−
粗銅の原料として、廃プリント基板、廃電子部品、廃電気部品を回収し、これらを、粉砕、篩い分けし、これを比重差、磁力、渦電流選別、静電選別により選別し、銅を濃縮回収して銅濃縮物とし、これを転炉で処理し、粗銅を得た。この粗銅の組成を表１に示す。なお、粗銅には、表１に記載の元素以外にも、Ｂｉ、Ｓ、Ｔｅ、Ｓｅ、Ａｕ、Ａｇ、Ｐｔなどが微量に含まれていた。
<Manufacture of copper solution>
-Preparation of crude copper-
As raw materials for crude copper, waste printed circuit boards, waste electronic components, and waste electrical components are collected, crushed and sieved, and sorted by specific gravity difference, magnetic force, eddy current sorting, and electrostatic sorting to concentrate copper. It collect | recovered and it was set as the copper concentrate, this was processed with the converter, and crude copper was obtained. The composition of this crude copper is shown in Table 1. In addition to the elements described in Table 1, the crude copper contained trace amounts of Bi, S, Te, Se, Au, Ag, Pt, and the like.
−粉体化処理−
次に、前記組成の粗銅を溶解炉にて溶融し、粗銅粉を得るためのアトマイズ処理を行った。
このアトマイズ処理に使用するアトマイズ装置は、図２に示すように溶融した粗銅を保持し、傾転できる保持炉から溶融した溶融銅を受け貯留するタンディッシュ１０と、該タンディッシュの底部より溶融銅流を流下して、該流下している溶融銅流に高圧の水を吐出して溶融銅を粉状化する噴霧部１２と、該噴霧部の下方には、粉状化した粗銅粉を冷却し、貯蔵し、搬出する貯蔵部１３とを有している。
このアトマイズ装置を用いて、前記粗銅１００ｋｇを１１３０℃で溶融銅が貯留されている保持炉からタンディッシュ内に溶融銅を受け、保温しながら、直径１３ｍｍの流下口より１０ｋｇ／ｍｉｎ〜１３ｋｇ／ｍｉｎで溶融銅流を流下して、流下された溶融銅流に対し３方吹きにより、水の圧力２０ＭＰａ、流速６８Ｌ／ｍｉｎで噴霧して、粗銅粉５０ｋｇを得た。このとき、ノズルより噴出させた水により、逆３角錐状を形成し、溶融銅流をその略中心部に流下した。
-Powdering treatment-
Next, the crude copper having the above composition was melted in a melting furnace, and an atomizing process for obtaining a coarse copper powder was performed.
As shown in FIG. 2, the atomizing apparatus used for this atomizing process holds the molten copper, receives the tundish 10 from the holding furnace capable of tilting and stores the molten copper, and the molten copper from the bottom of the tundish. A spraying part 12 for pulverizing molten copper by discharging high-pressure water into the flowing molten copper stream and cooling the pulverized coarse copper powder below the spraying part And a storage unit 13 for storing and unloading.
Using this atomizing device, 100 kg of the crude copper was received in a tundish from a holding furnace in which molten copper was stored at 1130 ° C., and while keeping the temperature, 10 kg / min to 13 kg / min from a downstream outlet having a diameter of 13 mm. Then, the molten copper flow was flowed down and sprayed at a water pressure of 20 MPa and a flow rate of 68 L / min by three-way blowing on the flow of molten copper flow to obtain 50 kg of crude copper powder. At this time, an inverted triangular pyramid shape was formed by the water ejected from the nozzle, and the molten copper flow was allowed to flow down to its substantially central portion.
得られた粗銅粉について、目開き１０６μｍの篩いで、篩って細粒粉側を１０６μｍアンダー粉として得た。この際、篩いを通過した粗銅粉質量を、篩いにかけた粗銅粉との全質量で除算し、割合を百分率にして篩い下移行率として求めたところ、９８質量％であった。また、篩いにより粒度分布を測定したところ、２５μｍ未満が６０質量％、２５μｍ以上４５μｍ未満が２２質量％、４５μｍ以上１０６μｍ未満が１６質量％、１０６μｍ以上が残部であった。
得られた１０６μｍアンダー粉の組成は、下記表２に示す通りであった。
The obtained coarse copper powder was sieved with a sieve having an opening of 106 μm, and the fine particle side was obtained as 106 μm under powder. At this time, the mass of the coarse copper powder that passed through the sieve was divided by the total mass of the coarse copper powder that had been sieved, and the percentage was obtained as a percentage, and it was 98 mass%. Further, when the particle size distribution was measured by sieving, 60% by mass was less than 25 μm, 22% by mass was 25 μm or more and less than 45 μm, 16% by mass was 45 μm or more but less than 106 μm, and the remainder was 106 μm or more.
The composition of the obtained 106 μm under powder was as shown in Table 2 below.
−銅溶解液の作製−
次に、作製した上記表２に示す篩い下の粗銅粉を、以下のようにして溶解して銅溶解液を作製した。
図６に示すように、銅溶解液を作製する溶解槽３０は、銅溶解液を貯留する溶解槽本体３１と、溶解槽本体の内側には、邪魔板３２が配置され、銅溶解液の攪拌のための攪拌機３３が配置されている。攪拌機３３は、回転数の制御可能とし、タービン羽４枚が１段となっている。また、貯留している液の温度の昇降、恒温制御を可能としている。溶解槽には、側壁に液の一部を流出し、沈殿槽３５に送液する配管３４がある。沈殿槽３５は、溶解槽３０で溶解し残った残粗銅粉が液とともに流入され、残粗銅粉を沈降させ、溶解槽３０に戻すポンプ３６を備えてある。図６中、３７は粗銅粉供給ホッパ、３８は酸化剤供給としてのエアー噴出器を表す。
-Preparation of copper solution-
Next, the prepared crude copper powder under the sieve shown in Table 2 was dissolved as follows to prepare a copper solution.
As shown in FIG. 6, the dissolution tank 30 for preparing the copper dissolution liquid includes a dissolution tank body 31 for storing the copper dissolution liquid, and a baffle plate 32 disposed inside the dissolution tank body, and stirring of the copper dissolution liquid. A stirrer 33 is arranged. The stirrer 33 can control the number of rotations, and four turbine blades are in one stage. In addition, the temperature of the stored liquid can be raised and lowered and controlled at a constant temperature. In the dissolution tank, there is a pipe 34 through which a part of the liquid flows out to the side wall and is sent to the precipitation tank 35. The settling tank 35 is provided with a pump 36 into which the remaining coarse copper powder that has been dissolved in the dissolving tank 30 flows in together with the liquid, precipitates the remaining coarse copper powder, and returns it to the dissolving tank 30. In FIG. 6, reference numeral 37 denotes a coarse copper powder supply hopper, and 38 denotes an air ejector as an oxidant supply.
溶解槽３０内には、硫酸銅溶液中の銅濃度が４０ｇ／Ｌ、遊離硫酸濃度１０ｇ／Ｌの液１００Ｌを用意し、これに、粗銅粉４．４ｋｇを添加し、攪拌しながら粗銅粉を溶解した。溶解槽の設定液温は６０℃として、１時間溶解反応した。
溶解を開始から数分間後には、溶解途中である残銅粉が浮遊してくるため、これを液とともに沈殿槽３５に送液する。そのため、配管３４の溶解槽３０側の開口は、銅溶解液液面付近が好ましい。沈殿槽３５では、攪拌機がないため残粗銅粉は送液後にすぐに沈降始め、沈殿槽の底部周辺に堆積する。これを底部より液とともに抜き出し、ポンプ３６を介して溶解槽３０に液と残粗銅粉を投入する。この際、溶解槽３０の底部に戻す。
図６に示すように、溶解槽３０に沈殿槽３５を配置し、この沈殿槽３５にて沈殿させた粗銅粉を溶解槽３０に送り、再度溶解反応をさせる。このように未溶解の粗銅粉を巡回させながら粗銅粉を溶解すると銅の溶解効率が顕著に向上し、溶解時間の短縮が可能となり、製造コストの大幅な削減が可能となる。
In the dissolution tank 30, 100 L of a liquid having a copper concentration of 40 g / L and a free sulfuric acid concentration of 10 g / L in a copper sulfate solution is prepared. To this, 4.4 kg of crude copper powder is added, and the crude copper powder is stirred and stirred. Dissolved. The set liquid temperature of the dissolution tank was 60 ° C., and the dissolution reaction was performed for 1 hour.
After several minutes from the start of dissolution, the remaining copper powder that is in the middle of dissolution floats, and is sent to the precipitation tank 35 together with the liquid. Therefore, the opening on the side of the dissolution tank 30 of the pipe 34 is preferably near the copper solution liquid surface. In the settling tank 35, since there is no stirrer, the remaining coarse copper powder begins to settle immediately after the liquid is fed and is deposited around the bottom of the settling tank. This is extracted together with the liquid from the bottom, and the liquid and the remaining coarse copper powder are put into the dissolution tank 30 via the pump 36. At this time, it is returned to the bottom of the dissolution tank 30.
As shown in FIG. 6, a precipitation tank 35 is disposed in the dissolution tank 30, and the crude copper powder precipitated in the precipitation tank 35 is sent to the dissolution tank 30 to cause a dissolution reaction again. When the crude copper powder is dissolved while circulating the undissolved crude copper powder in this manner, the copper dissolution efficiency is remarkably improved, the dissolution time can be shortened, and the manufacturing cost can be greatly reduced.
得られた銅溶解液に、表３に示す組成の粗銅粉を添加し、攪拌後、生成した沈殿を濾過により固液分離し、一次残渣を得た。得られた一次残渣の組成を表４に示す。また、銅溶解液の組成を表５に示す。 Crude copper powder having the composition shown in Table 3 was added to the obtained copper solution, and after stirring, the resulting precipitate was subjected to solid-liquid separation by filtration to obtain a primary residue. The composition of the obtained primary residue is shown in Table 4. Table 5 shows the composition of the copper solution.
（実験１）
次に、得られた銅溶解液に、粗銅粉を乾燥質量で２ｇ、４ｇ、１２ｇ、及び２４ｇ添加し、空気を液中に吹き込み、攪拌しながら銅溶解液中に粗銅粉を溶解して遊離硫酸（ＦＡ）濃度を低減化した。結果を表６に示す。液温は７５℃、反応時間は４時間とした。反応後は濾過し、濾液の銅濃度を電解用に調整すると銅電解用の銅電解液が得られた。
(Experiment 1)
Next, 2 g, 4 g, 12 g, and 24 g of crude copper powder are added to the obtained copper solution by dry mass, air is blown into the liquid, and the copper solution is dissolved and released while stirring. The sulfuric acid (FA) concentration was reduced. The results are shown in Table 6. The liquid temperature was 75 ° C. and the reaction time was 4 hours. After the reaction, the solution was filtered, and the copper concentration of the filtrate was adjusted for electrolysis to obtain a copper electrolyte for copper electrolysis.
これに対し、粗銅粉添加量が１２ｇ、及び２４ｇと多くなると遊離硫酸濃度（ＦＡ）が多くなり、砒素の除去ができなかった。
On the other hand, when the amount of added coarse copper powder increased to 12 g and 24 g, the free sulfuric acid concentration (FA) increased and arsenic could not be removed.
本発明の銅溶解液の浄液方法により製造された銅電解液は、銅電解における阻害元素である砒素等の不純物の含有量が少なく、適切な銅濃度に調整されているので、粗銅粉を用いた銅の製造方法に好適に用いられる。 The copper electrolyte produced by the copper solution purification method of the present invention has a low content of impurities such as arsenic, which is an inhibitory element in copper electrolysis, and is adjusted to an appropriate copper concentration. It is suitably used for the copper production method used.
１ 銅アノード
２ カソード
３ 銅電解液
４ 電解槽
１０ タンディッシュ
１１ 底部ノズル
１２ 噴霧部
１３ 貯蔵部
３０ 溶解槽
３１ 溶解槽本体
３２ 邪魔板
３３ 攪拌器
３５ 沈殿槽
１００ 噴射ノズル
１０１ 溶融銅流
DESCRIPTION OF SYMBOLS 1 Copper anode 2 Cathode 3 Copper electrolyte 4 Electrolysis tank 10 Tundish 11 Bottom nozzle 12 Spraying part 13 Storage part 30 Dissolution tank 31 Dissolution tank main body 32 Baffle plate 33 Stirrer 35 Precipitation tank 100 Injection nozzle 101 Molten copper flow
Claims (4)
前記浄液工程が、請求項１から３のいずれかに記載の銅溶解液の浄液方法により行われることを特徴とする銅の製造方法。The said liquid purification process is performed by the liquid purification method of the copper solution in any one of Claim 1 to 3, The manufacturing method of copper characterized by the above-mentioned.
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